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At least 55 records · Page 3

Radiation-induced alteration of apatite on the surface of Mars: first in situ observations with SuperCam Raman onboard Perseverance

Abstract Planetary exploration relies considerably on mineral characterization to advance our understanding of the solar system, the planets and their evolution. Thus, we must understand past and present processes that can alter materials exposed on the surface, affecting space mission data. Here, we analyze the first dataset monitoring the evolution of a known mineral target in situ on the Martian surface, brought there as a SuperCam calibration target onboard the Perseverance rover. We used Raman spectroscopy to monitor the crystalline state of a synthetic apatite sample over the first 950 Martian days (sols) of the Mars2020 mission. We note significant variations in the Raman spectra acquired on this target, specifically a decrease in the relative contribution of the Raman signal to the total signal. These observations are consistent with the results of a UV-irradiation test performed in the laboratory under conditions mimicking ambient Martian conditions. We conclude that the observed evolution reflects an alteration of the material, specifically the creation of electronic defects, due to its exposure to the Martian environment and, in particular, UV irradiation. This ongoing process of alteration of the Martian surface needs to be taken into account for mineralogical space mission data analysis.

Science & Technology - Other Topics↗

Coevolution of phyllosilicate, carbon, sulfide, and apatite in Ryugu's parent body

Abstract We analyzed an asteroid Ryugu sample returned to Earth by JAXA's Hayabusa2 mission using nanoIR, SEM, and TEM microscopy. We identified multiple distinct carbon reservoirs within the phyllosilicate matrix and demonstrate infrared spectral affinities for some of the carbon to insoluble organic matter (IOM). TEM studies of Ryugu samples have allowed us to better understand the interrelationship between the crystallographic orientations of phyllosilicates and the secondary minerals such as carbonate, sulfide, and apatite. Transport of elements provides a unifying theme for understanding these interrelationships.

Geochemistry & Geophysics↗

Pb-Apatite Framework as a Generator of Novel Flat-Band CuO-Based Physics

Based upon density functional theory (DFT) calculations, we present the basic electronic structure of CuPb 9 (PO 4 ) 6 O (Cu-doped lead apatite, aka LK-99), in two scenarios: (1) where the structure is constrained to the P3 symmetry and (2) where no symmetry is imposed. At the DFT level, the former is predicted to be metallic while the latter is found to be a charge-transfer insulator. In both cases the filling of these states is nominally d 9 , consistent with the standard Cu 2+ valence state, and Cu with a local magnetic moment of order 0.7 μ B . In the metallic case we find these states to be unusually flat (∼0.2 eV dispersion), giving a very high density of electronic states (DOS) at the Fermi level that we argue can be a host for novel electronic physics. The flatness of the bands is the likely origin of symmetry-lowering gapping possibilities that would remove the spectral weight from E F . Motivated by some initial experimental observations of metallic or semiconducting behavior, we propose that disorder (likely structural) is responsible for closing the gap. Here, we consider a variety of possibilities that could possibly close the charge-transfer gap but limit consideration to kinds of disorder that preserve electron count. Of the possible kinds we considered (spin disorder, O populating vacancy sites, and Cu on less energetically favorable Pb sites), the local Cu moment, and consequently the charge-transfer gap, remains robust. We conclude that disorder responsible for metallic behavior entails some kind of doping where the electron count changes. Further, we claim that the emergence of the flat bands should be due to weak wave function overlap between the orbitals on Cu and O sites, owing to the directional character of the constituent orbitals. Therefore, finding an appropriate host structure for minimizing hybridization between Cu and O while allowing them to still weakly interact should be a promising route for generating flat bands at E F which can lead to interesting electronic phenomena, regardless of whether LK-99 is a superconductor.

36 MATERIALS SCIENCE↗

Partitioning in REE-saturating minerals - Theory, experiment, and modelling of whitlockite, apatite, and evolution of lunar residual magmas

Compositions, including REEs determined by ion microprobe, of apatite and whitlockite in lunar rock assemblages rich in incompatible trace elements, are presented. Concentrations of REEs in lunar whitlockites are high, ranging from about 1.2 to 2.1 REEs (lanthanides + Y) per 56 oxygens. This slightly exceeds the level of two REE atoms per 56 oxygens at which the dominant substitution theoretically becomes saturated. This saturation effect leads to whitlockite REE(3+) D values at typical lunar whitlockite REE concentrations which are 30-40 percent lower than the D values at low concentrations. The halogen-to-phosphorous ratio in lunar melts is a key factor determining the REE distribution with crystalline assemblages. As long as P and REE concentrations of melts are in KREEP-like proportions, one or both of the phosphates will saturate in melts at similar REE concentrations.

Jolliff, Bradley L.↗

Calcium Solubility In Zeolite Synthetic-Apatite Mixtures

Life support systems at a lunar or martian outpost will require the ability to produce food growing in 1) treated lunar or martian regolith; 2) a synthetic soil, or 3) some combination of both. Zeoponic soil, composed of NH4 (-) and K-exchanged clinoptilolite (Cp) and synthetic apatite (Ap), can provide slow-release fertilization via dissolution and ion-exchange. Equilibrium studies indicate that KNH4, P, and Mg are available to plants at sufficient levels, however, Ca is deficient. Ca availability can be increased by adding a second Ca-bearing mineral: calcite (Cal); dolomite (Dol); or wollastonite (Wol). Additions of Cal, Dol, and Wol systematically change the concentrations of Ca and P in solution. Cal has the greatest effect, Dol the least, and Wol is intermediate.

Beiersdorfer, R.↗

Exhumation of Basement-cored Uplifts: Example of the Kyrgyz Range Quantified with Apatite Fission-track Thermochronology

The Kyrgyz Range, the northernmost portion of the Kyrgyzstan Tien Shan, displays topographic evidence for lateral propagation of surface uplift and exhumation. The highest and most deeply dissected segment lies in the center of the range. To the east, topography and relief decrease, and preserved remnants of a Cretaceous regional erosion surface imply minimal amounts of bedrock exhumation. The timing of exhumation of range segments defines the lateral propagation rate of the range-bounding reverse fault and quantifies the time and erosion depth needed to transform a mountain range from a juvenile to a mature morphology. New apatite fission-track (AFT) data from three transects from the eastern Kyrgyz Range, combined with published AFT data, demonstrate that the range has propagated over 110 km eastwards over the last 7-11 Myr. Based on the thermal and topographic evolutionary history, we present a model for a time-varying exhumation rate driven by rock uplift and changes in erodability and the time scale of geomorphic adjustment to surface uplift. Easily eroded, Cenozoic sedimentary rocks overlying resistant basement control early, rapid exhumation and slow surface upliftrates. As increasing amounts of resistant basement are exposed, exhumation rates decrease while surface uplift rates are sustained or increase, thereby growing topography. As the range becomes high enough to cause ice accumulation and develop steep river valleys, fluvial and glacial erosion become more powerful and exhumation rates once again increase. Independently determined range-noma1 shortening rates have also varied over time, suggesting a feedback between erosional efficiency and shortening rate.

Sobel, Edward R.↗

H-Isotopic Composition of Apatite in Northwest Africa 7034

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

McCubbin, F. M.↗

Carbonated apatite lattice parameter variation across incremental growth lines in teeth

Here, results of microbeam mapping (x-ray excited x-ray fluorescence and transmission x-ray diffraction) of Beluga whale cementum and of beaver dentin reveal growth bands are defined by variation in mineral content (carbonated hydroxyapatite, cAp), by variation in Zn content and by variation in cAp lattice parameter a. For both tissues, diffraction and fluorescence data show that Zn signal and a are anti-correlated, that is high Zn signal is co-located with low a, and vice versa. In cementum and bone, treatment with acid removes Ca, Zn and cAp. The data are strong evidence that Zn is incorporated into the cAp lattice in these tissues and that the amount of Zn incorporated varies across two very different types of growth bands, annual bands in Beluga cementum and daily incremental bands in beaver dentin. To the best of the authors’ knowledge, this is the first observation of spatial variation of lattice parameter within growth bands.

36 MATERIALS SCIENCE↗

Acid Vapor Weathering of Apatite and Implications for Mars

Phosphorus is an essential nutrient for terrestrial life, and therefore may be important in characterizing habitability on Mars. In addition, phosphate mobility on Mars has been postulated as an indicator of early aqueous activity [1]. Rock surfaces analyzed by the Spirit Mars Exploration Rover indicate elemental concentrations consistent with the loss of a phosphate-containing mineral [2], and the highly altered Paso Robles deposit contains ~5% P2O5, modeled as 8-10 % phosphate [3]. Depending on the pH of the solution, phosphate can exist as one of four charge states, which can affect its solubility, reactivity and mobility. Phosphate may therefore prove a useful and interesting tracer of alteration conditions on Mars. Acid vapor weathering has been previously studied as a potentially important process on Mars [4-6], and Paso Robles may have been formed by reaction of volcanic vapors with phosphate-bearing rock [3, 7]. Here we present preliminary results of acid vapor reactions in a Parr vessel [6] using fluorapatite, olivine and glass as single phases and in a mixture.

Hausrath, E. M.↗