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At least 757 records · Page 42

Characterizing the Effects of Thermal Profile and Gas Environment on the Heat Treatment of JSC-1A Lunar Simulant Using Combined Thermogravimetry and Mass Spectroscopy

As NASA strives towards a long duration presence on the Moon, it has become increasingly important to learn how to better utilize resources from the lunar surface for everything from habitats, vehicle infrastructure, and chemical extraction. To that end, a variety of lunar simulants have been sourced from terrestrially available volcanic minerals and glass as Apollo regolith is a finite resource unavailable for experimentation needing large masses. However, while mineralogy and chemical composition can approach that of lunar material in these simulants, there are still distinct non-lunar phases such as hydrates, carbonates, sulfates, and clays that can cause simulants to behave distinctly non-lunar in a variety of processing conditions that would ideally be applied to lunar material. Notably, severe glassy bubbling has been documented in a variety of vacuum sintering experiments on JSC-1A lunar Maria simulant heated via microwaves. The origins of this outgassing have not been well understood, but are normally attributed to the decomposition of non-lunar contaminates intrinsic to virtually all terrestrially sourced simulants. As such, a series of controlled environmental tests were performed to ascertain the origins of the high temperature outgassing and to develop heat treatments that can drive JSC-1A closer to lunar composition and behavior. It was found that in JSC-1A that distinct gas evolutions of water, carbon dioxide, and sulfur dioxide occur in both inert gas and vacuum. Additionally, the presence of hydrogen during heat treatments was shown to dramatically change gas evolutions, leading to distinctly more lunar-like composition and behavior from JSC-1A simulant.

sinter↗

Characterizing the Effects of Thermal Profile and Gas Environment on the Heat Treatment of JSC-1A Lunar Simulant Using Combined Thermogravimetry and Mass Spectroscopy

As NASA strives towards a long duration presence on the Moon, it has become increasingly important to learn how to better utilize resources from the lunar surface for everything from habitats, vehicle infrastructure, and chemical extraction. To that end, a variety of lunar simulants have been sourced from terrestrially available volcanic minerals and glass as Apollo regolith is a finite resource unavailable for experimentation needing large masses. However, while mineralogy and chemical composition can approach that of lunar material in these simulants, there are still distinct non-lunar phases such as hydrates, carbonates, sulfates, and clays that can cause simulants to behave distinctly non-lunar in a variety of processing conditions that would ideally be applied to lunar material. Notably, severe glassy bubbling has been documented in a variety of vacuum sintering experiments on JSC-1A lunar Maria simulant heated via microwaves. The origins of this outgassing have not been well understood, but are normally attributed to the decomposition of non-lunar contaminates intrinsic to virtually all terrestrially sourced simulants. As such, a series of controlled environmental tests were performed to ascertain the origins of the high temperature outgassing and to develop heat treatments that can drive JSC-1A closer to lunar composition and behavior. It was found that in JSC-1A that distinct gas evolutions of water, carbon dioxide, and sulfur dioxide occur in both inert gas and vacuum. Additionally, the presence of hydrogen during heat treatments was shown to dramatically change gas evolutions, leading to distinctly more lunar-like composition and behavior from JSC-1A simulant.

sinter↗

Constraining Alteration Processes Along the Siccar Point Unconformity in Gale Crater: Results from the Sample Analysis at Mars Instrument

A driving factor for sending the Mars Science Laboratory, Curiosity rover to Gale Crater was the orbital detection of clay minerals in the Glen Torridon (GT) region suggesting a past aqueous environment was habitable and could contain organic evidence of past microbiology. The objective of the Curiosity’s Sample Analysis at Mars (SAM)instrument was to detect organic evidence of past microbiology and volatile bearing mineralogy that would inform if past geochemical conditions would have supported microbiology in the GT region. The Siccar Point unconformity occurs between the underlying GT mudstone and the overlying Stimsons and stone of the Green heugh Pediment has evidence of enhanced alteration in the mudstone just below the contact suggestive of aqueous processes favorable for microbial activity. The origin of the altered material includes subaerial weathering, alteration from fluids moving along unconformity, upward fluid percolation from the mudstone or downward fluid percolation from the Pediment 1,2,3,4,5The objectives of this work were to 1) Utilize the S AM-EGA results to characterize the geochemistry and mineralogy above and below the Siccar Point unconformity through analysis of drilled samples in the3 GT mudstones and an overlying pediment sandstone. and 2) Utilize SAM-EGA results to constrain alteration scenario(s) below the unconformity.

B Sutter↗

TOI-1231 b: A Temperate, Neptune-sized Planet Transiting the Nearby M3 Dwarf NLTT 24399

We report the discovery of a transiting, temperate, Neptune-sized exoplanet orbiting the nearby (d = 27.5 pc), M3V star TOI-1231 (NLTT 24399, L 248-27, 2MASS J10265947-5228099). The planet was detected using photometric data from the Transiting Exoplanet Survey Satellite and followed up with observations from the Las Cumbres Observatory and the Antarctica Search for Transiting ExoPlanets program. Combining the photometric data sets, we find that the newly discovered planet has a radius of 3.65(+0.16,-0.15)Rꚛ and an orbital period of 24.246 days. Radial velocity measurements obtained with the Planet Finder Spectrograph on the Magellan Clay telescope confirm the existence of the planet and lead to a mass measurement of 15.5 ± 3.3 Mꚛ. With an equilibrium temperature of just 330 K, TOI-1231 b is one of the coolest small planets accessible for atmospheric studies thus far, and its host star's bright near-infrared brightness (J = 8.88, Ks = 8.07) makes it an exciting target for the Hubble Space Telescope and the James Webb Space Telescope. Future atmospheric observations would enable the first comparative planetology efforts in the 250–350 K temperature regime via comparisons with K2-18 b. Furthermore, TOI-1231's high systemic radial velocity (70.5 km/s) may allow for the detection of low-velocity hydrogen atoms escaping the planet by Doppler, shifting the H i Lyα stellar emission away from the geocoronal and interstellar medium absorption features.

Jennifer A. Burt↗

Laboratory Investigation of the Effect of Venusian Weathering on Mineral Spectra

Introduction: The recent selection of two missions to Venus has renewed the importance of deter-mining weathering reactions between minerals and the Venusian atmosphere, and the spectral signatures of minerals before, during, and after these reactions. The rate at which weathering reactions progress also constrain show long unstable minerals will be present on the surface (e.g., [1]), and enables the use of mineralogy as a constraint on surface age(e.g., [2-3]).In order to gain an understanding of how mineral compositions and spectra change with weathering, we have begun conducting experiments in a 1 atm experimental setup at Wesleyan University. This setup exposes minerals to the temperature and most abundant gases of the Venus atmosphere (CO2, SO2, N2).We conducted initial experiments using biotite, calcite, and montmorillonite in order to test our methodology with minerals that may be relevant to recording the history of water on Venus. Methods: Experiments were conducted in Thermo Fisher Scientific Lindberg/Blue M Mini-Mite horizontal tube furnaces at Wesleyan University. Experiments used natural mineral chips and powders, and were conducted at 1 atmosphere and 460 °C under pre-mixed gases provided by Air Gas(Table 1). The furnaces are set up in a flow through configuration so that solid samples are exposed to a fixed gas composition, and quartz glass process tubes were used in all experiments (1/4” diameter for experiment V4, ½” diameter for all others). These conditions were maintained for the du-rations listed in Table 1, at which point the furnace was turned off with gas flowing until the sample was cool enough to extract under N2and be placed in a desiccator for storage. Run products were carbon coated and examined using a Hitachi SU5000 Field Emission Gun Scanning Electron Microscope (SEM) equipped with an EDAX Octane Pro EDS detector located at Wesley-an University. Visible-Near Infrared Spectroscopy (VNIR) analysis was performed on powdered samples under a nitrogen atmosphere using an ASD Fieldspec Proover the 350-2500 nm range. Powdered mineral samples were milled to a particle size of < 45μm and were spiked with an internal standard (Al2O3, corundum) to obtain quantitative mineralogy. Samples were analyzed using a Panalytical X’Pert pro X-ray Diffractometer (XRD), with an X’Celerator high speed detector and Co Kα radiation, with data collected at a step size of 0.02 ̊/minute step counting rate from 2 to 80 degrees 2θ at 45 mA/40kV in the X-ray Diffraction Laboratory located at NASA Johnson Space Center. Materials Data Inc (MDI) software suite, JadeTMv9 was used for Rietveld refinement to determine phase abundances and mineral identification by comparing XRD patterns to International Center for Diffraction Data (ICDD) database patterns. Table 1: Experimental matrix. Experiment Name Duration (Days)Gas Com-position (trace gas)MineralsV487SO2/N2(1.4%)Montmorillonite, biotiteV519SO2/N2(1.4%)CalciteV619CO2/SO2/N2(1.4% SO2, 2.1% N2)Montmorillonite, biotiteV828SO2/N2(1.4%)Biotite, calcite Results: Calcite. In both experiments, calcite was exposed to the SO2/N2gas mixture, and in both experimental run products, XRD analysis detected anhydrite, which is consistent with EDS measurements conducted in the SEM. The XRD analyses show greater amounts of anhydrite present after 28 days than 19, suggesting the calcite reaction progressed further given longer duration. Grain surface morphology as seen in the SEM also shows secondary mineral growth (Fig. 1). VNIR spectra show no change, as expected since anhydrite lacks spectral features in this wavelength range. Montmorillonite. Montmorillonite was exposed to two different gas mixtures, the SO2/N2mix and CO2/SO2/N2mix over different durations (87 and 19 days, respectively). VNIR analyses of both run products show a reduction in the 1441and1910 nm water features as well as a shift of the 1411 and 2011 nm features to shorter wavelengths that may indicate re-structuring in the crystal lattice and the production of amorphous phases [4]. XRD results are consistent with this, showing a shift of the 001 peak from 15Åto 10Åin both run products. The amount of X-ray amorphous material in the montmorillonite run products was greater than that present in the unreacted clay, being the greatest in the 87 day V4 experiment. No other secondary phases were detected in the run products, however sulfur was present in EDS analyses of powder samples.

A R Santos↗

A Komatiite Succession as an Analog for the Olivine Bearing Rocks at Jezero

The Mars 2020 rover landed at Jezero crater on February 18, 2021 [1]. Since then, the rover has traveled around the “Séítah” region [2] and has collected data from the Mastcam-Z, Supercam, PIXL and SHERLOC instruments that has led to insights into the formation of the olivine-clay-carbonate bearing rocks that were identified from orbit [3,4]. Here we discuss three questions: 1) What have we learned about the olivine-claycarbonate unit? 2) What terrestrial analogs exist for the unit? 3) Why do the rocks have a thinly layered morphology? We shall briefly mention instrumental measurements which provide important information regarding the olivine bearing rock at Seitah. Note: Extended abstract included on attachment.

A.J. Brown↗

Air Sparge Pilot Study in the DNAPL Source Zone at Launch Complex 34

Multiple releases of trichloroethene (TCE) occurred at Launch Complex 34 (LC34) between the late 1950s and 1968. A 2007 conceptual site model estimated a 2-acre dense non-aqueous phase liquid (DNAPL) source area with mass in excess of 90,000 pounds, nearly 40 years after termination of launch activities. Located on a barrier island, LC34 currently has no complete exposure pathways and a historical groundwater flow radial from the DNAPL source zone (DSZ), the focus area of this study. The geology at LC34 is classified as Layers 1 through 9 with each layer representing a different lithology. These lithologies contribute to large variations in hydraulic conductivity (1x10-3 cm/sec to 1x10-8 cm/sec) with notable fine-grained units at Layer 4 (sandy clay) and Layer 7 (fine silty sand). Historically, technologies implemented at LC34 have been split vertically based on technology limitations and lithology. Remedial technologies have been evaluated to control and/or remediate the DSZ in the past; however, more aggressive technologies required significant cost and would likely leave considerable mass. Thus, an adaptive site management strategy has been implemented that adopts a treatment train approach which began in 2009 with hydraulic containment via pump and treat to control mass discharge from the DSZ while removing mass as a secondary benefit. Concurrently, hot spot areas in the larger dissolved plume are being treated by air sparging to reduce overall mass and the plume footprint. In 2019, a re-characterization of the DSZ was completed to update conditions in support of implementing more aggressive technologies as part of the treatment train approach. The results showed that the DSZ remained relatively the same size but with a slightly different morphology. Moreover, data showed that the fine-grained units (Layers 4 and 7) are storing most of the remaining mass, with TCE concentrations suggestive of DNAPL extending into Layer 7 (approximately 80 to 100 ft below land surface). Based on the current conditions, more aggressive technologies are still cost prohibitive; therefore, a different approach is warranted to determine the next implementable step in the treatment train. Air sparging is being proposed as a technology alternative based on several factors including lower treatment costs. A pilot study was conducted to test the feasibility of air sparging in the DSZ as the next step in the treatment train for that area.

Launch Complex 34↗

Recent Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument, Demonstrating a Watery Past

Curiosity landed in Gale crater August 2012 and has traversed (~27 km) sedimentary rocks that comprise a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. VSWIR spectra revealed the lowermost slopes of Mount Sharp contain mineral assemblages that are indicative of water-rock interactions (1-3), with sulfate-bearing units overlying phyllosilicate-bearing units. This mineralogical succession may mark the beginning of the transition from a relatively wet/warm to a very dry/cold Mars (e.g., 1, 4). Thirty-four powdered rock samples have been analyzed by the CheMin XRD instrument and mineralogical results from the first 6 years of the mission are reviewed in [5]. Here we describe the mineralogical diversity observed over the most recent 4 years. Sediments in the Vera Rubin Ridge (VRR) and Glen Torridon (GT) region were deposited in a lacustrine-fluvial environment and are syndepositional. The mineralogy suggests post-depositional fluid-rock interaction. Differences in mineralogy could have been the result of silica-poor, briny groundwater that destabilized smectite and precipitated hematite in VRR [6]. Other hypotheses include lake water-groundwater mixing or diagenesis driven by deeply sourced fluids altering smectite to precipitate hematite and amorphous silica. Preserved bedforms in the clay-sulfate transition region indicate a change from lacustrine-fluvial to aeolian depositional environments. Mineralogical changes include the identification of goethite along with the disappearance of phyllosilicate. The absence of crystalline Mg-sulfate in drilled samples from this transition region may mean that: 1) Sulfates are concentrated in secondary concretions not sampled by Curiosity’s drill, or 2) Sulfate components are either X-ray amorphous or if crystalline, became amorphous in the relatively low-humidity environment of the rover. Continued exploration of sulfate-rich rocks will elucidate this environmental transition above the phyllosilicate-rich sediments.

V M Tu↗

The breakup of a long-period comet is not a likely match to the Chicxulub impactor

Since the discovery of Ir in the clay layer at the K-Pg boundary, scientists have sought to constrain the origin of the extraterrestrial impactor that triggered the end-Cretaceous mass extinction of the non-avian dinosaurs and other species. While the first proposal was for an asteroid, for a while some theories invoked a cometary impactor to explain perceived periodicities in mass extinctions. Such models have long been disfavored by the mass of Ir in the layer, inferred to be 2.0−2.8×10^(11)cu.g. The size of the Chicxulub crater leads to an estimated asteroid impactor diameter, D≈10km. Comets typically impact at higher speeds, reducing the impactor mass for the same impact energy. Although it is increasingly recognized that a continuum exists between comets and asteroids, ’comets’ are considered to be more ice-rich (estimates for 67P/Churyumov-Gerasimenko are about 20%;), implying lower Ir contents per impactor mass. A carbonaceous chondrite-like asteroid of the appropriate size would likely deliver ≈2.3×10^(11)g of Ir, in the center of the estimated mass range of the global Ir layer; but a comet would only deliver ∼0.1×10^(11)g, because it would be less massive. Although these conclusions are long standing, Siraj and Loeb have recently argued anew in favor of a comet over an asteroid, based on dynamical and geochemical evidence. Here we demonstrate that their arguments are based on misinterpretations of the literature, and that an asteroid is in fact still highly favored over a comet.

Steven J. Desch↗

The breakup of a long-period comet is not a likely match to the Chicxulub impactor

Since the discovery of Ir in the clay layer at the K-Pg boundary [1], scientists have sought to constrain the origin of the extraterrestrial impactor that triggered the end-Cretaceous mass extinction of the non-avian dinosaurs and other species. While the first proposal was for an asteroid, for a while some theories invoked a cometary impactor to explain perceived periodicities in mass extinctions. Such models have long been disfavored by the mass of Ir in the layer, inferred to be2.0−2.8×1011g. The size of Chicxulub crater leads to an estimated asteroid impactor diameter,D≈10 km. Comets typically impact at higher speeds, reducing the impactor mass for the same impact energy. Although it is increasingly recognized that a continuum exists between comets and asteroids, ’comets’ are considered to be more ice-rich (estimates for67P/ Churyumov-Gerasimenko are about 20%;), implying lower Ir contents per impactor mass. A carbonaceous chondrite-like asteroid of the appropriate size would likely deliver≈2.3×1011gof Ir, in the center of the estimated mass range of the global Ir layer; but a comet would only deliver∼0.1×1011g, because it would be less massive. Although these conclusions are long standing, Siraj & Loeb have recently argued anew in favor of a comet over an asteroid, based on dynamical and geochemical evidence. Here we demonstrate that their arguments are based on misinterpretations of the literature, and that an asteroid is in fact still highly favored over a comet.

Steven J Desch↗

Mapping Organic-Mineral Associations in Jezero crater

The search for potential signs of life on Mars, a primary aim of the Mars 2020 mission, is greatly informed by the detection of organic matter1. The presence of organic matter also provides key information about the habitability and biological potential of the planet throughout its history. The Perseverance rover was designed for in situ science with the ability to collect a suite of promising samples for eventual return to Earth. One of its instruments, Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC), is a deep ultraviolet (DUV) Raman and fluorescence spectrometer designed to map the distribution of organic molecules and minerals on rock surfaces at a resolution of 100 μm2. With its unique spectral mapping capabilities, SHERLOC enables a novel understanding of organic-mineral relationships on Mars to better determine their formation, deposition, and preservation mechanisms. The rover’s landing site within Jezero crater combines a high potential for past habitability as the site of an ancient lake basin with a diverse set of minerals, including carbonates and clays, that may preserve organic materials and potential biosignatures. The Jezero crater floor includes three formations (fm); two of these, Máaz and Séítah, were explored as part of the mission’s first campaign. Here, we report the detection of multiple species of aromatic organic molecules using Raman and fluorescence spectroscopy across ten targets in the two formations. This is the first evidence of organic molecules in Martian materials obtained using Raman spectroscopy, and among the first using fluorescence spectroscopy, beyond Earth3. We report specific spatial patterns and classes of organic molecules in these compositionally distinct formations, potentially indicating different fates of carbon in these environments. Our findings indicate that there is a diversity of aromatic molecules prevalent on the Martian surface and these materials persist despite exposure to surface conditions. These organic molecules are largely found within minerals linked to aqueous processes, suggesting that these processes may have had a key role in organic synthesis, transport from their point of origin, or preservation.

Sunanda Sharma↗

WEATHERING ON VENUS: CONSTRAINTS FROM MODEL AND EXPERIMENTAL RESULTS

The surface of Venus is in contact with a hot (~470° C), high pressure (92 bars), and caustic (CO2 with S) atmosphere, which should cause progressive alteration of the crust [1, 2]. Alteration should form rock coatings of iron-oxides and sulfates, since water is not stable on the surface to make clay minerals [1, 3]. These coatings could, in theory, be used as a way to age date different lava flows, since the amount of alteration should correlate with the age of the rock exposed to the atmosphere [4, 5]. However, the exact alteration mineralogy and rate are still not well constrained [5]. Further, how the alteration mineralogy affects orbital emissivity measurements of the Venus surface is similarly not well understood [6]. Here we review the recent geochemical modeling [1, 7] and experimental [8-15] studies to constrain the main alteration minerals, potential alteration rates, and open questions about the surface mineralogy of Venus.

J. Filiberto↗

3d Particle Geometry Characterization of Apollo Regolith Samples Via Laser Diffraction and Dynamic Image Analysis

Establishing a fundamental understanding of regolith mechanics hinges on the characterization of the foundational physical parameters that dictate granular particle interactions both on micro- and macro-scales. Specifically, particle size distribution, particle geometry and grain density govern the geotechnical properties, including compressibility, shear strength, hydraulic conductivity (i.e., permeability), void ratio (i.e., porosity), and thermal conductivity of the lunar regolith. The absence of terrestrial geologic processes on the lunar surface, a lack of water, clay minerals, and organic material in lunar soils, and the narrow compositional range in terms of mineral diversity of the regolith produces a unique problem when attempting to project terrestrial soil mechanics concepts to the lunar surface. Additionally, the occurrence of agglutinates, exclusive to the lunar surface, further disassociates the physical behavior (e.g., particle crushability, flowability, etc.) of regolith from that observed in terrestrial soils.

R. Kovtun↗

Exploration of A Magma-Sediment Hydrothermal System on Earth: Constraints on the Habitability Potential of Martian Noachian Hydrothermal Systems

The martian crust is predominantly composed of basalt [1] and hosts a large variety of alteration materials caused by wide-ranging processes from volcanic hydrothermal processes to sedimentary and post-magmatic (e.g., see [2] and reference within). Specifically, there is an abundance of evidence that water previously flowed on Mars, ranging from ancient stream beds [3], lake basins [4], sedimentary fans in Jezero crater [5, 6], and clay minerals [7]. These secondary minerals have been observed by landers and rovers [2], from orbit [8], and in martian meteorites [9-11]. Along with low temperature alteration, high temperature hydrothermal systems from volcanic processes, as well as meteorite impacts, should have been present [12,13]. However, finding evidence of high-temperature hydrothermal activity has been challenging. To better understand these processes on Mars, Earth analogs can be used and then compared to potential scenarios and locations on Mars. Therefore, here we investigate a mafic dike and the surrounding metamorphic contact zone that has been hydrothermally altered from contact with ground water as it was emplaced. We will also compare our results to previous work on Robbers Roost Dike, an older mafic dike near our field location that intruded a similar protolith causing a potentially habitable hydrothermal system [14. 15].

R A Slank↗

MastCam Multispectral Examination of Rocks in the Sulfate-Bearing Terrain of Marker Band Valley, Gale Crater, Mars

A primary objective of the 4th extended mission of the Mars Science Laboratory rover Curiosity is to characterize the sulfate-bearing beds exposed on the slopes of Mt. Sharp (Aeolis Mons) above the clay-bearing beds of the Glen Torridon region characterized in the 3rd extended mission. Orbital reflectance spectroscopy from CRISM has indicated the presence of polyhydrated Mg sulfates in the portion of Mt. Sharp dubbed “Marker Band Valley” (MBV). The Marker Band is a darker toned, high-Ca pyroxene bearing unit that extends around much of Mt. Sharp above the first exposures of sulfate-bearing beds. Standoff imaging of the Marker Band indicates that it is not monolithic, but contains at least two subunits. Curiosity measures multispectral reflectance in the 430 to 1012 nm range with its Mastcam. While diagnostic spectral features of Mg-sulfates are not present in the Mastcam spectral range, a water overtone feature of some polyhydrated sulfates can be observed as a drop in reflectance in the longest wavelength one to three bands of Mastcam multispectral data. Other minerals associated with sulfate-generating alteration processes, most notably Fe-bearing minerals, are more readily detectable in Mastcam multispectral data.

W H Farrand↗

The Role of Olivine in Fe-Carbonate Formation in Gale Crater, Mars

Carbonates have been identified in remote sensing datasets, martian meteorites, and in-situ with rovers at Gale and Jezero craters. In Gale crater, traces of carbonate have been found by the SAM instrument throughout the Mars Science Laboratory mission, e.g., at Rocknest and Pahrump Hills, with models for carbonate formation at Pahrump Hills explored by [9]. Further up-section, CheMin data of clay-rich Glen Torridon (GT) samples show that five out of seven drill samples from GT contain Fe-carbonate alongside phyllosilicates. The GT sediments were deposited in a lacustrine environment and subsequently underwent multiple episodes of diagenesis. In this work, we explore the role of olivine in the formation of carbonates by modelling the interaction of different martian olivines with a previously modeled Gale groundwater. We then explore the incongruent dissolution of host rocks within the GT sediments by mixing olivine with quantities of the Kilmarie drill sample chemical composition as the reactant rock.

S M R Turner↗

Nitrogen in Ancient Mud: A Biosignature?

Nitrogen is an essential nutrient for all life on Earth and possibly elsewhere. Burial of nitrogen bound to organic matter constitutes the major flux of nitrogen into sediments today, which has led to the inference that nitrogen enrichments in sedimentary rocks may be a biosignature. However, abiotic processes such as lightning or volcanism can fix atmospheric N2 and contribute to sedimentary nitrogen burial in the absence of life. It is therefore uncertain whether observed nitrogen enrichments of up to 430 ppm in Paleoarchean metasedimentary biotite grains are indeed biogenic. This study seeks to address that problem with a numerical model. The NH4(+) concentration of an abiotic ocean is modeled as a function of source fluxes, pH-dependent NH3 volatilization, and equilibrated adsorption of NH4(+) onto clay particles. The results suggest that the observed nitrogen concentrations in Paleoarchean biotite can only be reconciled with purely abiotic processes if the ocean was more acidic (pH <6) and/or if the source fluxes from lightning and volcanism were at least an order of magnitude higher (≥10(exp 12) mol/yr) than previously thought. The bulk of the nitrogen is thus most likely of biological origin. While this does not necessitate a particular metabolism such as biological N2 fixation, the data provide evidence of nitrogen utilization back to 3.8 Gyr. Nitrogen abundances could thus provide useful information in extraterrestrial missions.

Early Earth↗

X-Ray Amorphous Sulfur-Bearing Phases in Sedimentary Rocks of Gale Crater, Mars

The Curiosity rover in Gale crater is investigating a mineral transition observed from orbit—an older “clay unit” to a younger “sulfate unit”—hypothesized to reflect the aridification of Mars' climate. Below this transition, the rover detected crystalline Ca-sulfates with minor Fe-sulfates but also found that some fraction of a rock's bulk SO 3 is often in the poorly constrained X-ray amorphous component. Here, we characterize the abundances and compositions of the X-ray amorphous sulfur-bearing phases in 19 drilled samples using a mass balance approach, and in a subset of 5 samples using evolved SO 2 gas measured using the SAM instrument. We find that ∼20–90 wt% of a sample's bulk SO 3 is in the X-ray amorphous state and that X-ray amorphous sulfur-bearing phase compositions are consistent with mixtures of Mg-S, Fe-S, and possibly Ca-S phases, likely sulfates or sulfites. These phases reside in the bedrock, perhaps as cementing agents deposited with detrital sediments or during early diagenesis, and in diagenetic alteration halos deposited after lithification during late diagenesis. The likely presence of highly soluble Mg-sulfates in the rocks suggests negligible fluid flow through the bedrock post-Mg-sulfate deposition. The X-ray amorphous sulfur-bearing phases probably became amorphous through dehydration in the current Martian atmosphere or inside the CheMin instrument. X-ray amorphous sulfur-bearing materials likely contribute to orbital spectral detections of sulfates, and so our results help form multiple hypotheses to be tested in the sulfate unit and are important for understanding the evolution of the Martian surface environment at Gale crater.

R. J. Smith↗