Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Fe(CoN)2”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

Materials Data on Fe(CoN)2 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

Materials Data on Fe(CoN)2 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗

The Valence of Iron in CM Chondrite Serpentine as Measured by Synchrotron Xanes

Fe-bearing phyllosilicates are the dominant product of aqueous alteration in carbonaceous chondrites, and serpentine is the most abundant phyllosilicate in CM2 chondrites that are the most abundant carbonaceous chondrite. Browning et al. predicted that Fe(3+)/(sum of Fe) ratios of serpentine in CM chondrites should change with progressive alteration. They proposed that progressive CM alteration is best monitored by evaluating the progress of Si and Fe3+ substitutions that necessarily attend the transition from end-member cronstedtite to serpentine. Their proposed Mineralogic Alteration Index, 2-(Fe(3+)/(2-Si)), was intended to highlight and utilize the relevant ex-change information in the stoichiometric phyllosilicate formulas based upon the coupled substitution of 2(Fe(3+), Al) = Si + (Mg, Fe(2+)...) in serpentine. The value of this ratio increases as alteration proceeds. We always wanted to directly test Browning s pre-diction through actual measurements of the Fe3+ con-tent of serpentine at the micron scale appropriate to EPMA analyses (Zega et al. have measured it at much finer scale), and this test can now be made using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). Thus, we have recently begun investigation with CMs that span a large portion of the range of observed aqueous alteration, and we first analyzed Murray, Nogoya, and ALH84029 by SR-XANES. However, we did not find clear correlation between Fe3+/(sum of Fe) ratios of serpentine and their alteration degrees. We thus analyzed serpentine in three more CMs and here report their Fe3+/(sum of Fe) ratios in comparison with our previous results.

Mikouchi, T.↗

Landing on Mercury: A Geochemical Perspective

The data from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft have revealed several surprising characteristics about the surface of Mercury, leading to its classification as a geochemical endmember among the terrestrial planets. Some of these features include elevated abundances of up to 3 wt% S, as much as 4 wt% C enrichment in low-reflectance materials (LRM) over the local mean, Na up to 5 wt% at high northern latitudes, and Fe abundances typically lower than 2 wt% [e.g., 1–4]. The S and Fe concentrations have been used to infer that Mercury’s igneous history evolved under highly reduced oxygen fugacity conditions between 2.6 and 7.3 log(sub 10) units below the iron–wüstite buffer [e.g., 5], which is more reducing than any other terrestrial planet in the solar system [e.g., 6]. This highly reduced nature has important con-sequences for the differentiation and thermal/magmatic evolution of Mercury. While the immense amount of data collected by MESSENGER revealed Mercury as a geochemical endmember, this new knowledge raised additional questions that necessitate continued exploration of the planet. Indeed, the joint ESA–JAXA dual-orbiter BepiColombo mission, launched in October 2018, is the most ambitious effort yet attempted to explore Mercury [e.g., 7]. Direct in situ elemental and mineralogical measurements on Mercury’s surface, however, are essential for addressing the new science questions that have arisen since MESSENGER.

K E Vander Kaaden↗

Hierarchically Porous M-N-C (M = Co and Fe) Single-Atom Electrocatalysts with Robust MN x Active Moieties Enable Enhanced ORR Performance

The great interest in fuel cells inspires a substantial amount of research on nonprecious metal catalysts as alternatives to Pt-based oxygen reduction reaction (ORR) electrocatalysts. In this work, bimodal template-based synthesis strategies are proposed for the scalable preparation of hierarchically porous M-N-C (M = Fe or Co) single-atom electrocatalysts featured with active and robust MN 2 active moieties. Multiscale tuning of M-N-C catalysts regarding increasing the number of active sites and boosting the intrinsic activity of each active site is realized simultaneously at a single-atom scale. In addition to the antipoisoning power and high affinity for O 2 , the optimized Fe-N-C catalysts with FeN 2 active site presents a superior electrocatalytic activity for ORR with a half-wave potential of 0.927 V (vs reversible hydrogen electrode (RHE)) in an alkaline medium, which is 49 and 55 mV higher than those of the Co-N-C counterpart and commercial Pt/C, respectively. Density functional theory calculations reveal that the FeN 2 site is more active than the CoN 2 site for ORR due to the lower energy barriers of the intermediates and products involved. In conclusion, the present work may help rational design of more robust ORR electrocatalysts at the atomic level, realizing the significant advances in electrochemical conversion and storage devices.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) is essential for affordable proton exchange membrane fuel cells. Herein, a new type of atomically dispersed Co doped carbon catalyst with a core–shell structure has been developed via a surfactant-assisted metal–organic framework approach. The cohesive interactions between the selected surfactant and the Co-doped zeolitic imidazolate framework (ZIF-8) nanocrystals lead to a unique confinement effect. During the thermal activation, this confinement effect suppressed the agglomeration of Co atomic sites and mitigated the collapse of internal microporous structures of ZIF-8. Among the studied surfactants, Pluronic F127 block copolymer led to the greatest performance gains with a doubling of the active site density relative to that of the surfactant-free catalyst. According to density functional theory calculations, unlike other Co catalysts, this new atomically dispersed Co–N–C@F127 catalyst is believed to contain substantial CoN 2+2 sites, which are active and thermodynamically favorable for the four-electron ORR pathway. The Co–N–C@F127 catalyst exhibits an unprecedented ORR activity with a half-wave potential (E 1/2 ) of 0.84 V (vs. RHE) as well as enhanced stability in the corrosive acidic media. It also demonstrated high initial performance with a power density of 0.87 W cm–2 along with encouraging durability in H 2 –O 2 fuel cells. The atomically dispersed Co site catalyst approaches that of the Fe–N–C catalyst and represents the highest reported PGM-free and Fe-free catalyst performance.

25 ENERGY STORAGE↗

Wildland Fire Induced Heating of Dome 375 Perma-Con®

AET-1 was tasked by ADEM with determining the temperature rise in the drum contents of drums stored in the Dome 375 Perma-Con® at TA-54 given a wildland fire. The wildland fire causes radiative and convective heating on the Perma-Con® exterior. The wildland fire time histories for the radiative and convective heating environment were provided to AET-1 by EES-16. If the calculated temperature rise results in a drum content temperature over 40 °C, then ADEM desires a design solution to ensure the peak temperature remains below 40 °C. An axi-symmetric FE simulation was completed to determine the peak temperature of the contents of a drum stored in the Dome 375 Perma-Con® during a wildland fire event. Three wildland fire time histories for the radiative and convective heat transfer were provided by EES-16 and were inputs for the FE simulation. The maximum drum content temperature reached was found to be 110 °C while using inputs from the SiteG_2ms_4ign_wind_from_west.xlsx time history input and not including the SWB in the model. Including the SWB in the results in a peak drum content temperature of 61 °C for the SiteG_2ms_4ign_wind_from_west.xlsx inputs. EES-16 decided that by using fuel mitigation efforts, such as mowing the grass and shrubs near the Perma-Con® they could reduce the shrub/grass fuel loading near the Perma-Con® from 1.46 kg/m 2 to 0.146 kg/m 2 and by using a less conservative fuel loading for the debris field inside the Dome 375 perimeter, reducing it from 0.58 kg/m2 to 0.058 kg/m 2 in their model. They also greatly increased the resolution of their radiation model and increased the accuracy of their model’s required convergence value. Using this refined input the maximum drum content temperature was found to be 28 °C with no SWB present in the model. Additionally, this refined input model was modified to include worst case emissivity values for the concrete, drum and Perma-Con® interior, along with adding a 91 second long residual radiative heat flux of 2,000 W/m2 to the end of the refined wildland fire input. For this case the maximum drum content temperature was found to be 32 °C. For Rev. 2 of this calculation and additional simulation was run that included a cable fire heat flux on the exterior of the Perma-Con® that was calculated by FP-DO. Including the cable fire heat flux in the model without the SWB resulted in a peak drum content temperature over time of 43 °C. Including the SWB in the simulation with the cable fire heat flux resulted in a peak drum content temperature over time of 35 °C.

42 ENGINEERING↗

Affordable Development and Demonstration of a Small NTR Engine and Stage: How Small is Big Enough?

The Nuclear Thermal Rocket (NTR) derives its energy from fission of uranium-235 atoms contained within fuel elements that comprise the engine's reactor core. It generates high thrust and has a specific impulse potential of approximately 900 seconds - a 100% increase over today's best chemical rockets. The Nuclear Thermal Propulsion (NTP) project, funded by NASA's AES program, includes five key task activities: (1) Recapture, demonstration, and validation of heritage graphite composite (GC) fuel (selected as the "Lead Fuel" option); (2) Engine Conceptual Design; (3) Operating Requirements Definition; (4) Identification of Affordable Options for Ground Testing; and (5) Formulation of an Affordable Development Strategy. During FY'14, a preliminary DDT&E plan and schedule for NTP development was outlined by GRC, DOE and industry that involved significant system-level demonstration projects that included GTD tests at the NNSS, followed by a FTD mission. To reduce cost for the GTD tests and FTD mission, small NTR engines, in either the 7.5 or 16.5 klbf thrust class, were considered. Both engine options used GC fuel and a "common" fuel element (FE) design. The small approximately 7.5 klbf "criticality-limited" engine produces approximately 157 megawatts of thermal power (MWt) and its core is configured with parallel rows of hexagonal-shaped FEs and tie tubes (TTs) with a FE to TT ratio of approximately 1:1. The larger approximately 16.5 klbf Small Nuclear Rocket Engine (SNRE), developed by LANL at the end of the Rover program, produces approximately 367 MWt and has a FE to TT ratio of approximately 2:1. Although both engines use a common 35 inch (approximately 89 cm) long FE, the SNRE's larger diameter core contains approximately 300 more FEs needed to produce an additional 210 MWt of power. To reduce the cost of the FTD mission, a simple "1-burn" lunar flyby mission was considered to reduce the LH2 propellant loading, the stage size and complexity. Use of existing and flight proven liquid rocket and stage hardware (e.g., from the RL10B-2 engine and Delta Cryogenic Second Stage) was also maximized to further aid affordability. This paper examines the pros and cons of using these two small engine options, including their potential to support future human exploration missions to the Moon, near Earth asteroids, and Mars, and recommends a preferred size. It also provides a preliminary assessment of the key activities, development options, and schedule required to affordably build, ground test and fly a small NTR engine and stage within a 10-year timeframe.

Spacecraft design↗

Affordable Development and Demonstration of a Small Nuclear Thermal Rocket (NTR) Engine and Stage: How Small Is Big Enough?

The Nuclear Thermal Rocket (NTR) derives its energy from fission of uranium-235 atoms contained within fuel elements that comprise the engine's reactor core. It generates high thrust and has a specific impulse potential of approximately 900 specific impulse - a 100 percent increase over today's best chemical rockets. The Nuclear Thermal Propulsion (NTP) project, funded by NASA's Advanced Exploration Systems (AES) program, includes five key task activities: (1) Recapture, demonstration, and validation of heritage graphite composite (GC) fuel (selected as the Lead Fuel option); (2) Engine Conceptual Design; (3) Operating Requirements Definition; (4) Identification of Affordable Options for Ground Testing; and (5) Formulation of an Affordable Development Strategy. During fiscal year (FY) 2014, a preliminary Design Development Test and Evaluation (DDT&E) plan and schedule for NTP development was outlined by the NASA Glenn Research Center (GRC), Department of Energy (DOE) and industry that involved significant system-level demonstration projects that included Ground Technology Demonstration (GTD) tests at the Nevada National Security Site (NNSS), followed by a Flight Technology Demonstration (FTD) mission. To reduce cost for the GTD tests and FTD mission, small NTR engines, in either the 7.5 or 16.5 kilopound-force thrust class, were considered. Both engine options used GC fuel and a common fuel element (FE) design. The small approximately 7.5 kilopound-force criticality-limited engine produces approximately157 thermal megawatts and its core is configured with parallel rows of hexagonal-shaped FEs and tie tubes (TTs) with a FE to TT ratio of approximately 1:1. The larger approximately 16.5 kilopound-force Small Nuclear Rocket Engine (SNRE), developed by Los Alamos National Laboratory (LANL) at the end of the Rover program, produces approximately 367 thermal megawatts and has a FE to TT ratio of approximately 2:1. Although both engines use a common 35-inch (approximately 89-centimeters) -long FE, the SNRE's larger diameter core contains approximately 300 more FEs needed to produce an additional 210 thermal megawatts of power. To reduce the cost of the FTD mission, a simple one-burn lunar flyby mission was considered to reduce the liquid hydrogen (LH2) propellant loading, the stage size and complexity. Use of existing and flight proven liquid rocket and stage hardware (e.g., from the RL10B-2 engine and Delta Cryogenic Second Stage) was also maximized to further aid affordability. This paper examines the pros and cons of using these two small engine options, including their potential to support future human exploration missions to the Moon, near Earth asteroids (NEA), and Mars, and recommends a preferred size. It also provides a preliminary assessment of the key activities, development options, and schedule required to affordably build, ground test and fly a small NTR engine and stage within a 10-year timeframe.

Spacecraft design↗

Effects of SO 2 poisoning and regeneration on spinel containing CH 4 oxidation catalysts

Methane oxidation under periodic conditions and the oxygen storage capacity of a bilayer Pt/Pd/Al 2 O 3 over a Mn 0.5 Fe 2.5 O 4 spinel catalyst were studied before and after SO 2 exposure, and after simulated regeneration conditions. Prior to sulfur exposure, improvement in CH 4 oxidation conversion under periodic conditions compared to steady-state conditions was observed. After sulfur exposure at 100 °C, there was a loss in CH 4 oxidation performance and a loss of oxygen storage capacity of the spinel material. Here, the extent of regeneration from sulfur poisoning depends on the ability to induce the decomposition of sulfate species, and while all regeneration methods tested in this study did improve CH 4 conversion, regeneration methods under periodic conditions induced greater sulfur species desorption from the catalyst surface leading to improved CH 4 con version. Key regeneration parameters – temperature, feed composition, modulation amplitude and frequency – were optimized to induce S species decomposition and correlated to CH 4 oxidation activity recovery.

03 NATURAL GAS↗

Phase formation, thermal stability and magnetic moment of cobalt nitride thin films

Cobalt nitride (Co-N) thin films prepared using a reactive magnetron sputtering process are studied in this work. During the thin film deposition process, the relative nitrogen gas flow (R{sub N{sub 2}}) was varied. As R{sub N{sub 2}} increases, Co(N), Co{sub 4}N, Co{sub 3}N and CoN phases are formed. An incremental increase in R{sub N{sub 2}}, after emergence of Co{sub 4}N phase at R{sub N{sub 2}} = 10%, results in a linear increase of the lattice constant (a) of Co{sub 4}N. For R{sub N{sub 2}} = 30%, a maximizes and becomes comparable to its theoretical value. An expansion in a of Co{sub 4}N, results in an enhancement of the magnetic moment, to the extent that it becomes even larger than pure Co. Such larger than pure metal magnetic moment for tetra-metal nitrides (M{sub 4}N) have been theoretically predicted. Incorporation of N atoms in M{sub 4}N configuration results in an expansion of a (relative to pure metal) and enhances the itinerary of conduction band electrons leading to larger than pure metal magnetic moment for M{sub 4}N compounds. Though a higher (than pure Fe) magnetic moment for Fe{sub 4}N thin films has been evidenced experimentally, higher (than pure Co) magnetic moment is evidenced in this work.

36 MATERIALS SCIENCE↗

Studies of Dirac and Weyl fermions by angle resolved photoemission spectroscopy

This dissertation consists of three parts. First, we study magnetic domains in Nd 2 Fe 14 B single crystals using high resolution magnetic force microscopy (MFM). In addition to the elongated, wavy nano-domains reported by a previous MFM study, we found that the micrometer size, star-shaped fractal pattern is constructed of an elongated network of nano-domains about 20 nm in width, with resolution-limited domain walls thinner than 2 nm. Second, we studied extra Dirac cones of multilayer graphene on SiC surface by ARPES and SPA-LEED. We discovered extra Dirac cones on Fermi surface due to SiC 6 x 6 and graphene 6√ 3 6√ 3 coincidence lattice on both single-layer and three-layer graphene sheets. We interpreted the position and intensity of the Dirac cone replicas, based on the scattering vectors from LEED patterns. We found the positions of replica Dirac cones are determined mostly by the 6 6 SiC superlattice even graphene layers grown thicker. Finally, we studied the electronic structure of MoTe 2 by ARPES and experimentally con rmed the prediction of type II Weyl state in this material. By combining the result of Density Functional Theory calculations and Berry curvature calculations with out experimental data, we identi ed Fermi arcs, track states and Weyl points, all features predicted to exist in a type II Weyl semimetal. This material is an excellent playground for studies of exotic Fermions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The breakdown of both strange metal and superconducting states at a pressure-induced quantum critical point in iron-pnictide superconductors

Here we report the first observation of the concurrent breakdown of the strange metal (SM) normal state and superconductivity at a pressure-induced quantum critical point in Ca 10 (Pt 4 As 8 )((Fe 0.97 Pt 0.03 ) 2 As 2 ) 5 superconductor. We find that, upon suppressing the superconducting state, the power exponent (α) changes from 1 to 2, and the slope of the temperature-linear resistivity per FeAs layer (A $\Box$ ) gradually diminishes. At a critical pressure, A $\Box$ and superconducting transition temperature (T c ) go to zero concurrently, where a quantum phase transition from a superconducting state with a SM normal state to a non-superconducting Fermi liquid state occurs. Scaling analysis reveals that the change of A $\Box$ with T c obeys the relation of T c ~ (A $\Box$ ) 0.5 , similar to what is seen in other chemically doped unconventional superconductors. These results suggest that there is a simple but powerful organizational principle of connecting the SM normal state with the high-T c superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hund's coupling assisted orbital-selective superconductivity in Ba1-xKxFe2As2

While the superconducting transition temperature of hole-doped Ba_{1-x}K_{x}Fe_{2}As_{2} decreases past optimal doping, superconductivity does not completely disappear even for the fully doped KFe_{2}As_{2} compound. In fact, superconductivity is robust through a Lifshitz transition where electron bands become hole-like around the zone corner at around x=0.7, thus challenging the conventional understanding of superconductivity in iron-based systems. High-resolution angle-resolved photoemission spectroscopy is used to investigate the superconducting gap structure, as well as the normal state electronic structure, around optimal doping and across the Lifshitz transition. Our findings reveal a largely orbital-dependent superconducting gap structure, where the more strongly correlated d_{xy} band has a vanishing superconducting gap at higher doping, aligning with the Hund's metal behavior observed in the normal state. Notably, the superconducting gap on the d_{xy} band disappears before the Lifshitz transition, suggesting that the Fermi surface topology may play a secondary role. We discuss how these results point to orbital-selective superconducting pairing and how strong correlations via Hund's coupling may shape superconducting gap structures in iron-based and other multiorbital superconductors.

FOS: Physical sciences↗

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. In this work, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e - ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm -2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.

25 ENERGY STORAGE↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗