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At least 685 records · Page 38

Assimilation of Fossil Hydrothermal Sulfide by Early Amazonian Martian Magmas: Implications for Ore Mineralization on Mars

Martian magmas would interact with any hydrosphere present, whether a global ocean [e.g., 1] or an icy (subterranean) hydrosphere [2] creating hydrothermal systems. Volcanogenic massive sulfide (VMS) ores, with Fe-Zn-Pb sulfides, created by hydrothermal deposition associated with a wide range of volcanism would be expected on Mars [3]. Similar to terrestrial komatiites, martian igneous rocks could generate orthomagmatic Ni-sulfide ore deposits by immiscible sulfide liquid segregation [4]. For this to occur, a martian magma would need to flow over (or intrude into) a pre-existing sulfur-rich formation. Here, we elaborate on the first evidence [5-6] of potential orthomagmatic mineralization in two Early Amazonian (2.4 Ga) igneous meteorites [7-8] involving a threestep process: i) formation of Fe-Zn-Pb sulfides, (ii) assimilated by the 2.4 Ga magmas leading to (iii) formation of orthomagmatic Ni-sulfide deposits. These deposits may remain on Mars, but the telltale signs of Zn-Pb enrichment and Ni-Co depletion in the two meteorites provide important insights into martian geology.

M Humayun↗

Atomic-scale mechanism of carbon nucleation from a deep crustal fluid by replica exchange reactive molecular dynamics simulation

Here we present a mechanistic model of carbon nucleation and growth from a fluid at elevated temperature (T) and pressure conditions, typical of those found in the shallow Earth’s lithosphere. Our model uses a replica exchange reactive molecular dynamics framework in which molecular configurations are swapped between adjacent T replica at regular intervals according to underlying statistical mechanics. This framework allows predicting complex molecular structures and thermodynamics while remaining computationally efficient. Here we simulate the reactivity of an unstable mixture of CO 2 and CH 4 at 1000 K and 1 GPa. We find that the path to thermodynamic equilibrium is initially entropy-driven, producing a diversity of short-lived species, including various alcohols with intermediate carbon oxidation states. Cyclic and polycyclic radicals that are sometimes resonance-stabilized form next and set the stage for carbon nucleation. The carbon exsolution process releases abundant water, is exothermic and starts with the nucleation of a large aggregate of hydrogenated graphene flakes from covalently bonded polycyclic units. The carbon backbone of this nucleus subsequently grows into a hydrogen-depleted fullerene-like structure, before evolving toward a partially bilayered graphene layer. Overall, our results show that the mechanism of graphitic C formation is certainly not bimolecular, and that it may involve a combination of key condensation and radical chain reactions. This will help understand the isotopic, and reactive characteristics of carbon-bearing fluids during their upward transit through the Earth’s mantle and crust. Moreover, the mechanistic insights outlined here present intriguing similarities with the process of soot and interstellar dust formation, which suggests that the widespread distribution of abiotic polyaromatic and graphitic material on Earth and beyond may reflect the prevalence of a fundamental chemical pathway.

58 GEOSCIENCES↗

The limits of palaeontological knowledge: finding the gold among the dross

Palaeontological interpretation rests on two interwoven sets of comparisons with the modern world. Palaeobiological interpretation relies on the placement of fossils within a phylogenetic and functional framework based primarily on the comparative biology of living organisms. Analogy to currently observable chemical, physical and taphonomic processes enables palaeoenvironmental inferences to be drawn from geological data. In older rocks, comparisons with the modern Earth can become tenuous, limiting palaeontological interpretation. The problem reaches its apogee in Archaean successions, yet pursuit of multiple lines of evidence establishes that complex microbial communities, fuelled by autotrophy and, likely, photoautotrophy, existed 3500 million years ago. Although Archaean palaeontology has to date focused on silicified coastal sediments, improved understanding of Earth's earliest biosphere may depend on the development of alternative environmental and taphonomic analogies. Spring precipitates and hydrothermal metal deposits are promising candidates. Terrestrial organisms may be of limited value in interpreting such fossils as may be found on Mars, although some points of comparison could prove general. Given limited opportunities for exploration, proper choice of environmental analogy is critical. Spring precipitates constitute excellent deposits for addressing questions of biology on another planet.

NASA Discipline Exobiology↗

High-temperature life without photosynthesis as a model for Mars

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.

Non-NASA Center↗

Construction of MoS 2 /NiS 2 heterostructure with fast interfacial reaction kinetics for ultrafast sodium storage

Constructing heterostructure is a valid method to reinforcing sodium storage performance of transition metal chalcogenides materials. Herein, a simple, safe and controllable one step hydrothermal method is proposed to synthesize MoS 2 /NiS 2 heterostructure. Due to the difference in band gaps and work functions of MoS 2 and NiS 2 , the charges are redistributed at the MoS 2 /NiS 2 heterointerfaces, thereby accelerating the migration of electrons and Na + . The heterointerfaces provide extra active sites for storing Na + , thus increasing the sodium storage capacity of the heterostructure. Furthermore, the distinct redox potentials of NiS 2 and MoS 2 promote the structural stability of MoS 2 /NiS 2 heterostructure during the electrochemical reaction processes. Consequently, the obtained MoS 2 /NiS 2 heterostructure exhibits superior rate properties (339.4 mAh g –1 at 10 A g –1 ) and ultra-stable cycling stability (480.5 mAh g –1 after 350 cycles at 1 A g –1 ). Finally, this paper presents a valid strategy for creating heterostructure anodes with excellent sodium storage properties.

25 ENERGY STORAGE↗

Solution processed high aspect ratio ultra-long vertically well-aligned ZnO nano scintillators for potential X-ray imaging applications

We report the photon (PL), electron (CL) and X-ray (XEL) induced luminescence characteristics of high aspect ratio ultra-long (~ 50 µm) ZnO nanorods (NRs) and discuss the potential for fast X-ray detection based on the consistent and efficient visible emission (~ 580 nm) from ZnO NRs. Nanostructured ZnO scintillators were rearranged to form a vertically well-aligned NR design in order to help light absorption and coupling resulting in luminescent and fast scintillation properties. The design of the nanorod array combines the key advantages of a low-cost growth technique together with environmentally friendly and widely available materials. A low temperature hydrothermal method was adopted to grow ZnO NRs in one cycle growth and their structural, optical and X-ray scintillation properties were investigated. The relatively short (~ 10 µm) ZnO NRs emitting in the near-band-edge region were found to be almost insensitive to X-rays. On the other hand, the higher XEL response of long ZnO NRs, which is a key parameter for evaluation of materials to be used as scintillators for high quality X-ray detection and imaging, along with a decay time response in the order of ns confirmed promising scintillation properties for fast and high-resolution X-ray detector applications.

47 OTHER INSTRUMENTATION↗

Editorial: Microbial C1 Metabolism and Biotechnology

Archaea and bacteria with the capacity to utilize one-carbon (C1) molecules as carbon and energy sources are widespread across the planet and are important players in many biogeochemical processes. As such, they occupy an array of diverse anaerobic and aerobic niches and perform unique metabolisms that enable the utilization of carbon dioxide (CO 2 ), carbon monoxide (CO), formate (HCOOH), methanol (CH 3 OH), and methane (CH 4 ) for growth. Several industrial processes have been developed that leverage these microbes for the targeted conversion of anthropogenic waste gases that contain C1 molecules, including natural gas (CH 4 ), anaerobic digestion-derived biogas (CH 4 and CO 2 ), industrial flue gas (CO 2 and CO), and syngas (CO 2 , CO, and H 2 ) (Figure 1). Further, there is increasing interest in electrochemical reduction of CO 2 to CO, CH 4 , and intermediates with increased solubility compared to gaseous C1 molecules (formate and methanol) using electrons derived from renewable sources like wind, solar, or hydrothermal systems to mitigate atmospheric greenhouse gas. Thus, C1-utilizing microbes will likely play an integral role in biotechnologies that are part of a sustainable, circular bioeconomy. However, fundamental knowledge gaps into the metabolism and physiology of these microbes exist that limit their utility as biocatalysts for carbon-efficient biomanufacturing. This special topic presents studies focused on the fundamental aspects of C1 metabolism in diverse microbial systems with the ability to convert anthropogenic greenhouse gases into valuable products.

59 BASIC BIOLOGICAL SCIENCES↗

Biomarkers as tracers for life on early earth and Mars

Biomarkers in geological samples are products derived from biochemical (natural product) precursors by reductive and oxidative processes (e.g., cholestanes from cholesterol). Generally, lipids, pigments and biomembranes are preserved best over longer geological times and labile compounds such as amino acids, sugars, etc. are useful biomarkers for recent times. Thus, the detailed characterization of biomarker compositions permits the assessment of the major contributing species of extinct and/or extant life. In the case of the early Earth, work has progressed to elucidate molecular structure and carbon isotropic signals preserved in ancient sedimentary rocks. In addition, the combination of bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems permits the modeling of the nature, behavior and preservation potential of primitive microbial communities. This approach uses combined molecular and isotopic analyses to characterize lipids produced by cultured bacteria (representative of ancient strains) and to test a variety of culture conditions which affect their biosynthesis. On considering Mars, the biomarkers from lipids and biopolymers would be expected to be preserved best if life flourished there during its early history (3.5-4 x 10(9) yr ago). Both oxidized and reduced products would be expected. This is based on the inferred occurrence of hydrothermal activity during that time with the concomitant preservation of biochemically-derived organic matter. Both known biomarkers (i.e., as elucidated for early terrestrial samples and for primitive terrestrial microbiota) and novel, potentially unknown compounds should be characterized.

Non-NASA Center↗

230Th Normalization: New Insights on an Essential Tool for Quantifying Sedimentary Fluxes in the Modern and Quaternary Ocean

230Th normalization is a valuable paleoceanographic tool for reconstructing high‐resolution sediment fluxes during the late Pleistocene (last ~500,000 years). As its application has expanded to ever more diverse marine environments, the nuances of 230Th systematics, with regard to particle type, particle size, lateral advective/diffusive redistribution, and other processes, have emerged. We synthesized over 1000 sedimentary records of 230Th from across the global ocean at two time slices, the late Holocene (0–5,000 years ago, or 0–5 ka) and the Last Glacial Maximum (18.5–23.5 ka), and investigated the spatial structure of 230Th‐normalized mass fluxes. On a global scale, sedimentary mass fluxes were significantly higher during the Last Glacial Maximum (1.79–2.17 g/sq.cmkyr, 95% confidence) relative to the Holocene (1.48–1.68 g/sq.cmkyr, 95% confidence). We then examined the potential confounding influences of boundary scavenging, nepheloid layers, hydrothermal scavenging, size‐dependent sediment fractionation, and carbonate dissolution on the efficacy of 230Th as a constant flux proxy. Anomalous 230Th behavior is sometimes observed proximal to hydrothermal ridges and in continental margins where high particle fluxes and steep continental slopes can lead to the combined effects of boundary scavenging and nepheloid interference. Notwithstanding these limitations, we found that 230Th normalization is a robust tool for determining sediment mass accumulation rates in the majority of pelagic marine settings (>1,000 m water depth).

Costa, Kassandra M.↗

Pronounced reduction in the regeneration energy of potassium sarcosinate CO 2 capture solvent using TiO 2

Absorption-based CO 2 capture technologies face economic feasibility concerns due to the exceedingly high energy requirements of solvent regeneration. Among various proposed solutions, solid acid-aided solvent regeneration stands out as a promising approach. Studies have shown that solid materials containing Lewis and Brønsted acid sites can facilitate deprotonation of protonated amine and breakdown of carbamate molecules, which significantly increases CO 2 desorption rate and decreases regeneration energy of common solvents such as MEA and DEA. However, the influence of solid acids on alternate solvents such as amino acids is not well known. Here, we report the performance of TiO 2 for the regeneration of CO 2 -loaded aqueous potassium sarcosinate (K-Sar) solvent. K-Sar is an environmentally friendly amino-acid salt that provides high CO 2 absorption rates, making it a good candidate for both point-source and direct-air capture. TiO 2 is hydrothermally stable and contains high surface acid site concentration. Desorption of CO 2 from K-Sar starts at room temperature in the presence of TiO 2 , while such onset temperature is greater than 70°C for regeneration without TiO 2 . Further, at a temperature of 95°C, the maximum CO 2 desorption rate and cumulative CO 2 removal increase by 128% and 91%, respectively, in the presence of TiO 2 compared to the no TiO 2 case. The total regeneration energy could be reduced by ~ 50% with TiO 2 , showcasing the significant role this process can take in improving the commercial competitiveness of absorption-based CO 2 capture. Further characterization with XRD, SEM, and NMR concluded that neither the TiO 2 powder nor the solvent undergoes any physical or chemical degradation in the regeneration process, suggesting the potential of their long-term usability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Life on Early Mars

Exploration of Mars has begun to unveil the history of the planet. Combinations of remote sensing, in situ compositional measurements and photographic observations have shown Mars had a dynamic and active geologic evolution. Mars geologic evolution encompassed conditions that were suitable for supporting life. A habitable planet must have water, carbon and energy sources along with a dynamic geologic past. Mars meets all of these requirements. The first 600 My of Martian history were ripe for life to develop because of the abundance of (i) Water- as shown by carved canyons and oceans or lakes with the early presence of near surface water shown by precipitated carbonates in ALH84001, well-dated at ~3.9 Gy, (ii) Energy from the original accretional processes, a molten core which generated a strong magnetic field leaving a permanent record in the early crust, active volcanism continuing throughout Martian history, and continuing impact processes, (iii) Carbon, water and a likely thicker atmosphere from extensive volcanic outgassing (i.e. H20, CO2, CH4, CO, O2, N2, H2S, SO2, etc.) and (iv) crustal tectonics as revealed by faulting and possible plate movement reflected by the magnetic pattern in the crust [1]. The question arises: "Why would life not develop from these favorable conditions on Mars in its first 600 My?" During this period, environmental near-surface conditions on Mars were more favorable to life than at any later time. Standing bodies of water, precipitation and flowing surface water, and possibly abundant hydrothermal energy would favor the formation of early life. (Even if life developed elsewhere on Earth, Venus, or on other bodies-it was transported to Mars where surface conditions were suitable for life to evolve). The commonly stated requirement that life would need hundreds of millions of year to get started is only an assumption; we know of no evidence that requires such a long interval for the development of life, if the proper habitable conditions are meet. Perhaps it could start in a very short interval during the first tens of millions of years after crustal formation. Even with impact-driven extinction events, such a short start-up time would allow life to restart multiple times until it persevered. If panspermia is considered, life could be introduced as soon as liquid surface water was present and could instantly thrive and spread.

Gibson, Everett K.↗

Early Mars: A Warm Wet Niche for Life

Exploration of Mars has begun to unveil the history of the planet. Combinations of remote sensing, in situ compositional measurements and photographic observations have shown Mars had a dynamic and active geologic evolution. Mars geologic evolution had conditions that were suitable for supporting life. A habitable planet must have water, carbon and energy sources along with a dynamic geologic past. Mars meets all of these requirements. The first 600 Ma of Martian history were ripe for life to develop because of the abundance of: (i) Water-as shown by carved canyons and oceans or lakes with the early presence of near surface water shown by precipitated carbonates in ALH84001, well-dated at approx.3.9 Ga, (ii) Energy from the original accretional processes, a molten core which generated a strong magnetic field leaving a permanent record in the early crust, active volcanism continuing throughout Martian history, and continuing impact processes, (iii) Carbon, water and a likely thicker atmosphere from extensive volcanic outgassing (i.e. H2O, CO2, CH4, CO, O2, N2, H2S, SO2, etc.) and (iv) crustal tectonics as revealed by faulting and possible plate movement reflected by the magnetic patterns in the crust [1]. The question arises: "Why would life not develop from these favorable conditions on Mars in its first 600 Ma?" During this period, environmental near-surface conditions on Mars were more favorable to life than at any later time. Standing bodies of water, precipitation and flowing surface water, and possibly abundant hydrothermal energy would favor the formation of early life. (Even if life developed elsewhere on Earth, Venus, or on other bodies-it was transported to Mars where surface conditions were suitable for life to evolve)

Gibson, Everett K.↗

Divergent Responses of Carbon Nitride Dot‐Based Amorphous Species and Small Molecule Hybrids to Trace Level Analytes

Bottom-up synthesis of carbon nitride dots (CNDs) offers a versatile platform for the creation of diverse nanomaterials with tunable properties. Here, we report a facile hydrothermal approach using citric acid (CA) and urea (U) as precursors to synthesize CNDs with varying degrees of condensation and crystallinity. By carefully controlling reaction conditions and post-synthetic treatments, we obtained two distinct fractions: a polycrystalline fraction composed of small-molecule hybrids and an amorphous fraction containing CNDs. We then sought to understand how the dominant species in these fractions impact sensing abilities using trace-level explosive exemplars. In conclusion, the results have important implications for sensing and related applications where understanding the complex interplay between synthetic conditions and post-synthetic processing play vital roles in determining the final properties of CND materials.

carbon nitride dots↗

Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS 2 for Catalyzing Ammonia Synthesis

Dinitrogen conversion to ammonia via electrochemical reduction with over 10% Faradaic efficiency is demonstrated in this work. Co-doped MoS 2-x polycrystalline nanosheets with S vacancies as the catalysts are loaded onto carbon cloth by hydrothermal growth from Mo, Co, and S precursors. A sulfur vacancy on the MoS 2-x basal plane mimicking the natural Mo-nitrogenase active site is modified by Co doping and exhibits superior dinitrogen-to-ammonia conversion activity. Density-functional simulation reveals that the free energy barrier, which can be compensated by applied overpotential, is reduced from 1.62 to 0.59 eV after Co doping. Meanwhile, dinitrogen tends to be chemically adsorbed to defective MoS 2-x , which effectively activates the dinitrogen molecule for the dissociation of the N≡N triple bond. Here, this process is further accelerated by Co doping, resulting from the modulation of Mo–N bonding configuration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Revisiting the West Clearwater Lake Impact Structure, Canada

The West and East Clearwater Lake impact structures are two of the most distinctive and recognizable impact structures on Earth. Known regionally as the "Clearwater Lake Complex", these structures are located in northern Quebec, Canada (56 deg 10 N, 74 deg 20 W) approximately 125 km east of Hudson Bay. The currently accepted diameters are 36 km and 26 km for the West and East structures, respectively. Long thought to represent a rare example of a double impact, recent age dating has called this into question with ages of approximately 286 Ma and approximately 460-470 Ma being proposed for the West and East structures, respectively. Relatively little is known about the East Clearwater Lake structure. There is no surface exposure and what information there is comes from geophysics and two drill cores obtained in the 1960s. In contrast, the West Clearwater Lake structure is relatively well preserved with large ring of islands in the approximately 30 km diameter lake. Much of the work done on West Clearwater stems from field investigations carried out in 1977 driven by the Apollo program, with a focus on the impact melt rocks and other impactites, which are well exposed on the ring of islands. To our knowledge, the Clearwater Lake impact structures have not been the focus of detailed impact geology field investigations since the 1977 expedition and the only geological map that exists is from the 1960s and is at the reconnaissance level. Our knowledge of impact cratering processes have increased substantially since this time, as have the analytical techniques available for samples. This provided the motivation for a joint Canadian-US-UK expedition to the West Clearwater Lake impact structure in August and September 2015, under the auspices of the FINESSE (Field Investigations to Enable Solar System Science and Exploration) project, part of NASA's Solar System Exploration Research Virtual Institute (SSERVI). We focus here on the impactites of the West Clearwater Lake impact structure. Other ongoing studies, also presented at this conference, focus on central uplift formation, the impact-generated hydrothermal system, xxxx and using WCIS as an analog test site for crew studies of sampling protocols].

West Clearwater Lake↗

Soluble Organic Matter Molecular Atlas of Ryugu Reveals Cold Hydrothermalism on C-Type Asteroid Parent Body

The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration.

Asteroids, comets and Kuiper belt↗

Conditions on Early Mars Might Have Fostered Rapid and Early Development of Life

The exploration of Mars during the past decades has begun to unveil the history of the planet. The combinations of remote sensing, in situ geochemical compositional measurements and photographic observations from both above and on the surface have shown Mars to have a dynamic and active geologic evolution. Mars geologic evolution clearly had conditions that were suitable for supporting life. For a planet to be able to be habitable, it must have water, carbon sources, energy sources and a dynamic geologic past. Mars meets all of these requirements. The first 600 My of Martian history were ripe for life to develop because of the abundance of (i) Water-carved canyons and oceans or lakes with the early presence of near surface water shown by precipitated carbonates in ALH84001 well-dated at approx.3.9 Gy., (ii) Energy from the original accretional processes, a molten core which generated a strong magnetic field leaving a permanent record in the early crust, early active volcanism continuing throughout Martian history, and, and continuing impact processes, (iii) Carbon and water from possibly extensive volcanic outgassing (i.e. H2O, CO2, CH4, CO, O2, N2, H2S, SO2, etc.) and (iv) some crustal tectonics as revealed by faulting and possible plate movement reflected by the magnetic pattern in the crust. The question arises: "Why would life not evolve from these favorable conditions on early Mars in its first 600 My?" During this period, it seems likely that environmental near-surface conditions on Mars were more favorable to life than at any later time. Standing bodies of water, precipitation and flowing surface water, and possibly abundant hydrothermal energy would all favor the formation of early life. Even if life developed elsewhere (on Earth, Venus, or on other solar systems) and was transported to Mars, the surface conditions were likely very hospitable for that introduced life to multiply and evolve.

Gibson, Everett K.↗

Effective use of principal component analysis with high resolution remote sensing data to delineate hydrothermal alteration and carbonate rocks

Methods of applying principal component (PC) analysis to high resolution remote sensing imagery were examined. Using Airborne Imaging Spectrometer (AIS) data, PC analysis was found to be useful for removing the effects of albedo and noise and for isolating the significant information on argillic alteration, zeolite, and carbonate minerals. An effective technique for using PC analysis using an input the first 16 AIS bands, 7 intermediate bands, and the last 16 AIS bands from the 32 flat field corrected bands between 2048 and 2337 nm. Most of the significant mineralogical information resided in the second PC. PC color composites and density sliced images provided a good mineralogical separation when applied to a AIS data set. Although computer intensive, the advantage of PC analysis is that it employs algorithms which already exist on most image processing systems.

Feldman, Sandra C.↗