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Abstract
In order to gain insights on the conditions of aqueous alteration on asteroid Ryugu and the origin of water in the outer solar system, we developed the measurement of water content in magnetite at the micrometer scale by secondary ion mass spectrometry (NanoSIMS) and determined the H and Si content of coarse-grained euhedral magnetite grains (polyhedral magnetite) and coarse-grained fibrous (spherulitic) magnetite from the Ryugu polished section A0058-C1001. The hydrogen content in magnetite ranges between similar to 900 and similar to 3300 wt ppm equivalent water and is correlated with the Si content. Polyhedral magnetite has low and homogenous silicon and water content, whereas fibrous magnetite shows correlated Si and water excesses. These excesses can be explained by the presence of hydrous Si-rich amorphous nanoinclusions trapped during the precipitation of fibrous magnetite away from equilibrium and testify that fibrous magnetite formed from a hydrous gel with possibly more than 20 wt% water. An attempt to determine the water content in sub-mu m framboids indicates that additional calibration and contamination issues must be addressed before a safe conclusion can be drawn, but hints at elevated water content as well. The high water content in fibrous magnetite, expected to be among the first minerals to crystallize at low water-rock ratio, points to the control of water content by local conditions of magnetite precipitation rather than large-scale alteration conditions. Systematic lithological variations associated with water-rich and water-poor magnetite suggest that the global context of alteration may be better understood if local water concentrations are compared with millimeter-scale distribution of the various morphologies of magnetite. Finally, the high water content in the magnetite precursor gel indicates that the initial O isotopic composition in alteration water must not have been very different from that of the earliest magnetite crystals.
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Abstract
The northern Eastern Cordillera (EC) in the Colombian Andes is a wide (-200 km) high-elevation (> 2.5 km) subduction-related asymmetric plateau. This plateau is currently subjected to shortening and magmatic addition, and yet the nature of the lowermost crust and its transition to the underlying mantle remains poorly constrained. To improve our knowledge about the structure of the deep crust beneath the EC plateau, we conducted a joint inversion of travel times of local earthquakes and gravity data. Gravity contributes to up to 0.5% in dVp and dVs with no affectation of the shape or location of the discussed anomalies. Along the latitudinal profile with the highest resolution (similar to 5.7(degrees)N), two anomalies are identified at depths of 40-60 km beneath the plateau. A western low-velocity anomaly is interpreted as crustal material underthrust eastward beneath the northwestern EC. This process is triggering the abrupt change in topography between the adjacent low-elevation basin and the orogenic plateau. Additionally, a high-velocity anomaly beneath the eastern flank of the EC is likely related to mantle metasomatism and westward underthrusting of the foreland lithosphere. This metasomatism is either related to the interaction between mafic magmas and the uppermost mantle or silica enrichment that occurred during a past episode of flat subduction. Evidence for foreland underthrusting includes relocated earthquakes at 33-42 km depth within the thrust system between the EC and the foreland, along with increased shortening in the eastern part of the plateau, an increase in exhumation rates, the eastward migration of deformation towards the foreland, and dominated thick-skinned deformation in the upper crust of the foreland with an eastward vergence of thrusts and related folds. Furthermore, within the central part of the plateau, our results show low velocities between 30 and 40 km depth, consistent with previous constraints, suggesting magmatic underplating beneath the Paipa-Iza volcanic complex.
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Abstract
Boron substitution represents a promising approach to stabilize carbon clathrate structures, but no thermodynamically stable substitution schemes have been identified for frameworks other than the type-VII (sodalite) structure type. To investigate the possibility for additional tetrahedral carbon-based clathrate networks, more than 5000 unique boron decoration schemes were investigated computationally for type-I and type-II carbon clathrates with a range of guest elements including Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba. Density functional theory calculations were performed at 10 and 50 GPa, and the stability and impact of boron substitution were evaluated. The results indicate that the boron-substituted carbon clathrates are stabilized under high-pressure conditions. Full cage occupancies of intermediate-sized guest atoms (e.g., Na, Ca, and Sr) are the most favorable energetically. Clathrate stability is maximized when the boron atoms are substituted within the hexagonal rings of the large [5(12)6(2)]/[5(12)6(4)] cages. Several structures with favorable formation enthalpies <-200 meV/atom were predicted, and type-I Ca8B16C30 is on the convex hull at 50 GPa. This structure represents the first thermodynamically stable type-I clathrate identified and suggests that boron-substituted carbon clathrates may represent a large family of diamond-like framework materials with a range of structure types and guest/framework substitutions.
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Abstract
O-GlcNAcylation is a critical post-translational modification of proteins observed in both plants and animals and plays a key role in growth and development. While considerable knowledge exists about over 3000 substrates in animals, our understanding of this modification in plants remains limited. Unlike animals, plants possess two putative homologs: SECRET AGENT (SEC) and SPINDLY, with SPINDLY also exhibiting O-fucosylation activity. To investigate the role of SEC as a major O-GlcNAc transferase in plants, we utilized lectin-weak affinity chromatography enrichment and stable isotope labeling in Arabidopsis labeling, quantifying at both MS1 and MS2 levels. Our findings reveal a significant reduction in O-GlcNAc levels in the sec mutant, indicating the critical role of SEC in mediating O-GlcNAcylation. Through a comprehensive approach, combining higher-energy collision dissociation and electron-transfer high-energy collision dissociation fragmentation with substantial fractionations, we expanded our GlcNAc profiling, identifying 436 O-GlcNAc targets, including 227 new targets. The targets span diverse cellular processes, suggesting broad regulatory functions of O-GlcNAcylation. The expanded targets also enabled exploration of crosstalk between O-GlcNAcylation and O-fucosylation. We also examined electron-transfer high-energy collision dissociation fragmentation for site assignment. This report advances our understanding of O-GlcNAcylation in plants, facilitating further research in this field.
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Abstract
Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U6+ mineral localities surpasses the number of U4+ mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U6+ mineral localities increases earlier in the Phanerozoic than the number of U4+ sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U6+-U4+. Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U4+ uraninite (UO2) formation from weathered granite and basalt. Louvain network community detection shows that U6+ forms minerals with many more shared elements and redox states than U4+. The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEECV) values of U6+ minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEECV values of U4+ minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U6+ minerals compared to S6+ minerals illustrates the importance of the development of land plants, organic matter deposition, and redox-controlled U deposition from ground water in continental sediments during this time-period.
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Abstract
The Gemini Planet Imager (GPI) has excelled in imaging debris disks in the near-infrared. The GPI Exoplanet Survey imaged 24 debris disks in polarized H-band light, while other programs observed half of these disks in polarized J and/or K1 bands. Using these data, we present a uniform analysis of the morphology of each disk to find asymmetries suggestive of perturbations, particularly those due to planet-disk interactions. The multiwavelength surface brightness, disk color, and geometry permit the identification of any asymmetries such as warps or disk offsets from the central star. We find that 19 of the disks in this sample exhibit asymmetries in surface brightness, disk color, disk geometry, or a combination of the three, suggesting that for this sample, perturbations, as seen in scattered light, are common. The relationship between these perturbations and potential planets in the system is discussed. We also explore correlations among stellar temperatures, ages, disk properties, and observed perturbations. We find significant trends between the vertical aspect ratio and the stellar temperature, disk radial extent, and the dust grain size distribution power law, q. We also confirm a trend between the disk color and stellar effective temperature, where the disk becomes increasingly red/neutral with increasing temperature. Such results have important implications for the evolution of debris disk systems around stars of various spectral types.
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Abstract
The Transiting Exoplanet Survey Satellite (TESS) mission delivers time-series photometry for millions of stars across the sky, offering a probe into stellar astrophysics, including rotation, on a population scale. However, light-curve systematics related to the satellite's 13.7 day orbit have prevented stellar rotation searches for periods longer than 13 days, putting the majority of stars beyond reach. Machine-learning methods have the ability to identify systematics and recover robust signals, enabling us to recover rotation periods up to 35 days for GK dwarfs and 80 days for M dwarfs. We present a catalog of 7245 rotation periods for cool dwarfs in the Southern Continuous Viewing Zone, estimated using convolutional neural networks. We find evidence for structure in the period distribution consistent with prior Kepler and K2 results, including a gap in 10-20 day cool-star periods thought to arise from a change in stellar spin-down or activity. Using a combination of spectroscopic and gyrochronologic constraints, we fit stellar evolution models to estimate masses and ages for stars with rotation periods. We find strong correlations between the detectability of rotation in TESS and the effective temperature, age, and metallicity of the stars. Finally, we investigate the relationships between rotation and newly obtained spot filling fractions estimated from Apache Point Observatory Galactic Evolution Experiment spectra. Field starspot filling fractions are elevated in the same temperature and period regime where open clusters' magnetic braking stalls, lending support to an internal shear mechanism that can produce both phenomena.
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Abstract
Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads-one-dimensional diamondoid polymers formed through the compression of small molecules-represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid. The resulting product possesses high-density, pendant carboxyl functionalization along both sides of the backbone, enabling new opportunities for the post-synthetic processing and chemical modification of nanothread materials applicable to a broad range of potential applications.
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Abstract
Sulfur plays a major role in martian geochemistry and sulfate minerals are important repositories of water. However, their hydration states on Mars are poorly constrained. Therefore, understanding the hydration and distribution of sulfate minerals on Mars is important for understanding its geologic, hydrologic, and atmospheric evolution as well as its habitability potential. NASA's Perseverance rover is currently exploring the Noachian-age Jezero crater, which hosts a fan-delta system associated with a paleolake. The crater floor includes two igneous units (the Seitah and Maaz formations), both of which contain evidence of later alteration by fluids including sulfate minerals. Results from the rover instruments Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry and Planetary Instrument for X-ray Lithochemistry reveal the presence of a mix of crystalline and amorphous hydrated Mg-sulfate minerals (both MgSO4 center dot[3-5]H2O and possible MgSO4 center dot H2O), and anhydrous Ca-sulfate minerals. The sulfate phases within each outcrop may have formed from single or multiple episodes of water activity, although several depositional events seem likely for the different units in the crater floor. Textural and chemical evidence suggest that the sulfate minerals most likely precipitated from a low temperature sulfate-rich fluid of moderate pH. The identification of approximately four waters puts a lower constraint on the hydration state of sulfate minerals in the shallow subsurface, which has implications for the martian hydrological budget. These sulfate minerals are key samples for future Mars sample return.
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Abstract
Bacterial genome dynamics are vital for understanding the mechanisms underlying microbial adaptation, growth, and their broader impact on host phenotype. Structural variants (SVs), genomic alterations of 10 base pairs or more, play a pivotal role in driving evolutionary processes and maintaining genomic heterogeneity within bacterial populations. While SV detection in isolate genomes is relatively straightforward, metagenomes present broader challenges due to absence of clear reference genomes and presence of mixed strains. In response, our proposed method rhea, forgoes reference genomes and metagenome-assembled genomes (MAGs) by encompassing a single metagenome coassembly graph constructed from all samples in a series. The log fold change in graph coverage between subsequent samples is then calculated to call SVs that are thriving or declining throughout the series. We show rhea to outperform existing methods for SV and horizontal gene transfer (HGT) detection in two simulated mock metagenomes, which is particularly noticeable as the simulated reads diverge from reference genomes and an increase in strain diversity is incorporated. We additionally demonstrate use cases for rhea on series metagenomic data of environmental and fermented food microbiomes to detect specific sequence alterations between subsequent time and temperature samples, suggesting host advantage. Our innovative approach leverages raw read patterns rather than references or MAGs to include all sequencing reads in analysis, and thus provide versatility in studying SVs across diverse and poorly characterized microbial communities for more comprehensive insights into microbial genome dynamics.
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