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NASA NTRS2015

Major Volatiles from MSL SAM Evolved Gas Analyses: Yellowknife Bay Through Lower Mount Sharp

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of <150 μm fines from five sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform ("RN") and drilled Sheepbed mudstone from sites John Klein ("JK") and Cumberland ("CB"). One was drilled from the Windjana ("WJ") site on a sandstone of the Kimberly formation investigated on route to Mount Sharp. Another was drilled from the Confidence Hills ("CH") site on a sandstone of the Murray Formation at the base of Mt. Sharp (Pahrump Hills). Outcrops are sedimentary rocks that are largely of fluvial or lacustrine origin, with minor aeolian deposits.. SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments. The identity and evolution temperature (T) of evolved gases can support CheMin mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with XRD (e.g., X-ray amorphous phases). They can also give constraints on sample organic chemistry. Here, we discuss trends in major evolved volatiles from SAM EGA analyses to date.

McAdam, A. C.↗
NASA NTRS2013

A Habitable Fluvio-Lacustrine Environment at Yellowknife Bay, Gale Crater, Mars

The Curiosity rover discovered fine-grained sedimentary rocks, which are inferred to represent an ancient lake and preserve evidence of an environment that would have been suited to support a martian biosphere founded on chemolithoautotrophy. This aqueous environment was characterized by neutral pH, low salinity, and variable redox states of both iron and sulfur species. Carbon, hydrogen, oxygen, sulfur, nitrogen, and phosphorus were measured directly as key biogenic elements; by inference, phosphorus is assumed to have been available. The environment probably had a minimum duration of hundreds to tens of thousands of years. These results highlight the biological viability of fluvial-lacustrine environments in the post-Noachian history of Mars.

Mars↗
NASA NTRS2015

Clays and Carbonates in a Groundwater-Fed 3.8 Ga Martian Lake: Insights to Subsurface Habitability on Mars

On Earth, the deep biosphere remains a largely unexplored, but clearly important carbon reservoir. Results from some uplifted central peaks in craters on Mars indicate that substantial carbon was also present at depth and might have helped sustain a deep biosphere. In fact, many factors relevant to deep biosphere habitability are more favorable on Mars than on Earth (e.g. porosity of the crust, geothermal gradient). Future exploration of Mars should include landing sites where materials have been exhumed from depth by meteor impact or basins where subsurface fluids have emerged, carrying clues to subsurface habitability. One of the most astrobiologically interesting sites on Mars McLaughlin Crater, a 93 km-diameter impact crater that formed approximately 4 b.y. ago. On the floor of the crater is a stratigraphic section of subhorizontal, layered sedimentary rocks with strong spectroscopic evidence for Fe-rich clay minerals and Mg-rich carbonates, which we interpret as ancient lacustrine deposits. The fluids that formed these materials likely originated in the subsurface, based on the paucity of channels leading into the crater basin and the fact that this is one of the deepest basins on Mars - a good candidate to have experienced upwelling of subsurface fluids. Therefore, the deposits within McLaughlin crater provide insight into subsurface processes on Mars. In this presentation, we will discuss the habitability of the martian subsurface as well as the geology of McLaughlin Crater and the possibility to detect biomarkers at that site with a future landed mission.

Michalski, Joseph↗
NASA NTRS2016

Acid Sulfate Alteration on Mars

A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

Ming, D. W.↗
NASA NTRS2016

Authigenesis/Diagenesis of the Murray Formation Mudstone in Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August, 2012. The rover has traversed up section through approximately 150 m of sedimentary rocks deposited in fluvial, deltaic, and lacustrine environments (Bradbury group and overlying Mount Sharp group). The Murray formation lies at the base of the Mt. Sharp group and has been interpreted to be a finely laminated mudstone likely deposited in a subaqueous lacustrine environment. Four drill samples from several elevations in the Murray fm have been acquired by the rover's sampling system and delivered to the CheMin XRD instrument. The lower section of the Murray fm contains 2:1 phyllosilicate(s), hematite, jarosite, XRD amorphous materials, and primary basaltic minerals. Further up section, the Murray fm contains magnetite, cristobalite, tridymite, abundant Si-rich XRD amorphous materials along with plagioclase and K-feldspars. Murray formation materials appear to have been altered under an open hydrologic system based on the bulk chemistry of these materials measured by the Alpha Particle X-ray Spectrometer (APXS). The 2:1 phyllosilicate only occurs in the lowermost section of the Murray fm and may be detrital or formed during authigenesis of Murray fm materials, similar to the Fe-saponite and magnetite detected in a mudstone in the Yellowknife Bay fm near Curiosity's landing site (stratigraphically at the base of the Bradbury group). The occurrence of jarosite and hematite in the lower section indicates an acidic diagenetic event. These phases may have formed via several acidic alteration mechanisms, including (1) oxidative weathering of mafic igneous rocks containing sulfides; (2) sulfuric acid weathering of Fe-bearing phases; and (3) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity. The transition from abundant hematite in the lowermost Murray fm to magnetite moving up section may indicate changes in lake chemistry, i.e., variable redox conditions, possibly during authigenesis or subsequent diagenetic events. Tridymite, a high temperature mineral, (and possibly cristobalite) is detrital, potentially deposited in a lake from a distal silicic volcanic rock source or from crustal materials present prior to the Gale Crater impact event. Abundant Si-rich XRD amorphous materials in the upper sections of the Murray fm may be detrital or an aqueous alteration product of primary igneous phases and phyllosilicates. Curiosity's science team is still deciphering the authigenesis and diagenetic events that formed the Murray fm. The mineralogy and geochemistry of the formation suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions.

Ming, D. W.↗
NASA NTRS2016

Diagenesis Along Fractures in an Eolian Sandstone, Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August 2012. The rover has traversed up section through approx.100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation lies unconformable over a lacustrine mudstone at the base of the Mount Sharp group and has been interpreted to be a cross-bedded sandstone of lithified eolian dunes. Mineralogy of the unaltered Stimson sandstone consists of plagioclase feldspar, pyroxenes, and magnetite with minor abundances of hematite, and Ca-sulfates (anhydrite, bassanite). Unaltered sandstone has a composition similar to the average Mars crustal composition. Alteration "halos" occur adjacent to fractures in the Stimson. Fluids passing through these fractures have altered the chemistry and mineralogy of the sandstone. Silicon and S enrichments and depletions in Al, Fe, Mg, Na, K, Ni and Mn suggest aqueous alteration in an open hydrologic system. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes, but less abundant in the altered compared to the unaltered Stimson sandstone and lower pyroxene/plagioclase feldspar. The mineralogy and geochemistry of the altered sandstone suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).

Ming, D. W.↗
NASA NTRS2016

Is Tridymite at Gale Crater Evidence for Silicic Volcanism on Mars?

The X-ray diffraction (XRD) instrument (CheMin) onboard the MSL rover Curiosity detected 17 wt% of the SiO2 polymorph tridymite (relative to bulk sample) for the Buckskin drill sample (73 wt% SiO2) obtained from sedimentary rock in the Murray formation at Gale Crater, Mars. Other detected crystalline materials are plagioclase, sanidine, cristobalite, cation-deficient magnetite, and anhydrite. XRD amorphous material constitutes approx. 60 wt% of bulk sample, and the position of its broad diffraction peak near approx. 26 deg. 2-theta is consistent with opal-A. Tridymite is a lowpressure, high-temperature mineral (approx. 870 to 1670 deg. C) whose XRD-identified occurrence on the Earth is usually associated with silicic (e.g., rhyolitic) volcanism. High SiO2 deposits have been detected at Gale crater by remote sensing from martian orbit and interpreted as opal-A on the basis H2O and Si-OH spectral features. Proposed opal-A formation pathways include precipitation of silica from lake waters and high-SiO2 residues of acid-sulfate leaching. Tridymite is nominally anhydrous and would not exhibit these spectral features. We have chemically and spectrally analyzed rhyolitic samples from New Mexico and Iwodake volcano (Japan). The glassy (by XRD) NM samples have H2O spectral features similar to opal-A. The Iwodake sample, which has been subjected to high-temperature acid sulfate leaching, also has H2O spectral features similar to opal-A. The Iwodake sample has approx. 98 wt% SiO2 and 1% wt% TiO2 (by XRF), tridymite (>80 wt.% of crystalline material without detectable quartz by XRD), and H2O and Si-OH spectral features. These results open the working hypothesis that the opal-A-like high-SiO2 deposits at Gale crater detected from martian orbit are products of alteration associated with silicic volcanism. The presence or absence of tridymite will depend on lava crystallization temperatures (NM) and post crystallization alteration temperatures (Iwodake).

Morris, Richard V.↗
NASA NTRS2016

The Sample at Mars Analysis (SAM) Detections of CO2 and CO in Sedimentary Material from Gale Crater, Mars: Implications for the Presence of Organic Carbon and Microbial Habitability on Mars

Sedimentary rock samples heated to 860 C in the SAM instrument evolved CO2 and CO indicating the presence of organic-carbon(C) in Gale Crater materials. Martian or exogenous (meteoritic, interplanetary dust) CO2 and CO could be derived from combustion of simple organics (less than 300 C), complex refractory organics/amorphous carbon (300-600 C), and/or magmatic carbon (greater than 600 C) as result of thermal decomposition of Gale Crater perchlorates, and sulfates present that produce O2. Oxidized organic compounds could also evolve CO2 and CO over broad temperature range (150 to 800 C) and such organics are expected on Mars via exogenous sources. Alternatively, organic-C could also have been oxidized to carboxylic acids [e.g, mellitic acid (RCOOH), acetate (CH3CO2(-)), and oxalates ((2)C2O4(-))] by oxidative radiolytic weathering, or other oxidation processes. The presence of oxidized organics is consistent with the limited detection of reduced organic-C phases by the SAM-gas chromatography. Organic-C content as determined by CO2 and CO contents could range between 800 and 2400 ppm C indicating that substantial organic-C component is present in Gale Crater. There are contributions from SAM background however, even in worse case scenarios, this would only account for as much as half of the detected CO2 and CO. Nevertheless, if organic-C levels were assumed to have existed in a reduced form on ancient Mars and this was bioavailable C, then less than 1% of C in Gale Crater sediments could have supported an exclusively heterotrophic microbial population of 1 x 10(exp 5) cells/g sediment (assumes 9 x 10(exp -7) microgram/cell and 0.5 micrograms C/microgram cell). While other essential nutrients (e.g., S and P) could be limiting, organic-C contents, may have been sufficient to support limited heterotrophic microbial populations on ancient Mars.

Sutter, Brad↗
NASA NTRS2016

Elemental Gains/Losses Associated with Alteration Fractures in an Eolian Sandstone, Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has traversed up section through approximately 100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation unconformably overlies a lacustrine mudstone at the base of the Mount Sharp group and has been interpreted to be a cross-bedded sandstone of lithified eolian dunes. Unaltered Stimson sandstone has a basaltic composition similar to the average Mars crustal composition, but is more variable and ranges to lower K and higher Al. Fluids passing through alteration "halos" adjacent to fractures have altered the chemistry and mineralogy of the sandstone. Elemental mass gains and losses in the alteration halos were quantified using immobile element concentrations, i.e., Ti (taus). Alteration halos have elemental gains in Si, Ca, S, and P and large losses in Al, Fe, Mn, Mg, Na, K, Ni, and Zn. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes. The igneous phases were less abundant in the altered sandstone with a lower pyroxene/plagioclase feldspar. Large elemental losses suggest acidic fluids initially removed these elements (Al mobile under acid conditions). Enrichments in Si, Ca, and S suggest secondary fluids (possibly alkaline) passed through these fractures leaving behind X-ray amorphous Si and Ca-sulfates. The mechanism for the large elemental gains in P is unclear. The geochemistry and mineralogy of the altered sandstone suggests a complicated diagenetic history with multiple episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).

Ming, D. W.↗
NASA NTRS2016

Ground Truthing Orbital Clay Mineral Observations with the APXS Onboard Mars Exploration Rover Opportunity

NASA's Mars Exploration Rover Opportunity has been exploring approximately 22 km diameter Endeavour crater since 2011. Its rim segments predate the Hesperian-age Burns formation and expose Noachian-age material, which is associated with orbital Fe3+-Mg-rich clay mineral observations [1,2]. Moving to an orders of magnitude smaller instrumental field of view on the ground, the clay minerals were challenging to pinpoint on the basis of geochemical data because they appear to be the result of near-isochemical weathering of the local bedrock [3,4]. However, the APXS revealed a more complex mineral story as fracture fills and so-called red zones appear to contain more Al-rich clay minerals [5,6], which had not been observed from orbit. These observations are important to constrain clay mineral formation processes. More detail will be added as Opportunity is heading into her 10th extended mission, during which she will investigate Noachian bedrock that predates Endeavour crater, study sedimentary rocks inside Endeavour crater, and explore a fluid-carved gully. ESA's ExoMars rover will land on Noachian-age Oxia Planum where abundant Fe3+-Mg-rich clay minerals have been observed from orbit, but the story will undoubtedly become more complex once seen from the ground.

Schroeder, C.↗
NASA NTRS2016

Microbial Habitability in Gale Crater: Sample Analysis at Mars (SAM) Instrument Detection of Microbial Essential Carbon and Nitrogen

Chemical analyses of Mars soils and sediments from previous landed missions have demonstrated that Mars surface materials possessed major (e.g., P, K, Ca, Mg, S) and minor (e.g., Fe, Mn, Zn, Ni, Cl) elements essential to support microbial life. However, the detection of microbial essential organic-carbon (C) and nitrate have been more elusive until the Mars Science Laboratory (MSL) rover mission. Nitrate and organic-C in Gale Crater, Mars have been detected by the Sample Analysis at Mars (SAM) instrument onboard the MSL Curiosity rover. Eolian fines and drilled sedimentary rock samples were heated in the SAM oven from approximately 30 to 860 degrees Centigrade where evolved gases (e.g., nitrous oxide (NO) and CO2) were released and analyzed by SAM’s quadrupole mass spectrometer (MS). The temperatures of evolved NO was assigned to nitrate while evolved CO2 was assigned to organic-C and carbonate. The CO2 releases in several samples occurred below 450 degrees Centigrade suggesting organic-C dominated in those samples. As much as 7 micromoles NO3-N per gram and 200 micromoles CO2-C per gram have been detected in the Gale Crater materials. These N and C levels coupled with assumed microbial biomass (9 x 10 (sup -7) micrograms per cell) C (0.5 micrograms C per micrograms cell) and N (0.14 micrograms N per micrograms cell) requirements, suggests that less than 1 percent and less than 10 percent of Gale Crater C and N, respectively, would be required if available, to accommodate biomass requirements of 1 by 10 (sup 5) cells per gram sediment. While nitrogen is the limiting nutrient, the potential exists that sufficient N and organic-C were present to support limited heterotrophic microbial populations that may have existed on ancient Mars.

Sutter, B.↗
NASA NTRS2016

The Sample at Mars Analysis (SAM) Detections of CO2 and CO in Sedimentary Material from Gale Crater, Mars: Implications for the Presence of Organic Carbon and Microbial Habitability on Mars

Sedimentary rock samples heated to 860 degrees Centigrade in the SAM (Sample at Mars) instrument evolved CO2 and CO indicating the presence of organic-carbon(C) in Gale Crater materials. Martian or exogenous (meteoritic, interplanetary dust) CO2 and CO could be derived from combustion of simple organics (less than 300 degrees Centigrade), complex refractory organics/amorphous carbon (300-600 degrees Centigrade), and/or magmatic carbon (greater than 600 degrees Centigrade) as result of thermal decomposition of Gale Crater perchlorates, and sulfates present that produce O2. Oxidized organic compounds could also evolve CO2 and CO over broad temperature range (150 to 800 degrees Centigrade) and such organics are expected on Mars via exogenous sources. Alternatively, organic-C could also have been oxidized to carboxylic acids [e.g, mellitic acid (RCOOH), acetate (CH3CO2-), and oxalates (C2O42-)] by oxidative radiolytic weathering, or other oxidation processes. The presence of oxidized organics is consistent with the limited detection of reduced organic-C phases by the SAM-gas chromatography. Organic-C content as determined by CO2 and CO contents could range between 800 and 2400 parts per million C indicating that substantial organic-C component is present in Gale Crater. There are contributions from SAM background however, even in worst-case scenarios, this would only account for as much as half of the detected CO2 and CO. Nevertheless, if organic-C levels were assumed to have existed in a reduced form on ancient Mars and this was bioavailable C, then less than 1 percent of C in Gale Crater sediments could have supported an exclusively heterotrophic microbial population of 1 by 10 (sup 5) cells per gram sediment (assumes 9 by 10 (sup -7) microgram per cell and 0.5 micrograms C per microgram cell). While other essential nutrients (e.g., S and P) could be limiting, organic-C contents, may have been sufficient to support limited heterotrophic microbial populations on ancient Mars.

Sutter, Brad↗
NASA NTRS2014

Scratching the Surface of Martian Habitability

Earth and Mars, though formed at the same time from the same materials, look very different today. Early in their histories they evolved through some of the same processes, but at some point their evolutionary paths diverged, sending them in perhaps irrevocably different directions. Knowledge of the factors that contributed to such different outcomes will help to determine how planets become habitable and how common habitable planets may be. The Mars surface environment is harsh today, but in situ measurements of ancient sedimentary rock by Mars Science Laboratory reveal chemical and mineralogical evidence of past conditions that might have been more favorable for life to exist. But chemistry is only part of what is required to make an environment habitable. Physical conditions constrain the chemical reactions that underlie life processes; the chemical and physical characteristics that make planets habitable are thus entangled.

Mars rover↗
NASA NTRS2017

Calcium Sulfates at Gale Crater and Limitations on Gypsum Stability

The Mars Science Laboratory rover has been exploring sedimentary rocks of the Bradbury group and overlying Murray formation, as well as the unconformably overlying Stimson formation. Early in exploration, and continuing to present, there have been observations of many Ca-sulfate veins that cut all three stratigraphic units. The CheMin XRD instrument on Curiosity provides complete mineralogy for drilled or scooped samples, with explicit identification of gypsum, bassanite, and anhydrite (crystal structure of so-called "soluble anhydrite," or gamma-CaSO4, is so similar to bassanite that it can't be distinguished at CheMin 2-theta resolution; here we refer to these similar dehydrated forms simply as bassanite).

Vantiman, D. T.↗
NASA NTRS2017

X-Ray Diffraction on Mars: Scientific Discoveries Made by the CheMin Instrument

The Mars Science Laboratory Curiosity landed in Gale crater in August 2012 with the goal to identify and characterize habitable environments on Mars. Curiosity has been studying a series of sedimentary rocks primarily deposited in fluviolacustrine environments approximately 3.5 Ga. Minerals in the rocks and soils on Mars can help place further constraints on these ancient aqueous environments, including pH, salinity, and relative duration of liquid water. The Chemistry and Mineralogy (CheMin) X-ray diffraction and X-ray fluorescence instrument on Curiosity uses a Co X-ray source and charge-coupled device detector in transmission geometry to collect 2D Debye-Scherrer ring patterns of the less than 150 micron size fraction of drilled rock powders or scooped sediments. With an angular range of approximately 2.52deg 20 and a 20 resolution of approximately 0.3deg, mineral abundances can be quantified with a detection limit of approximately 1-2 wt. %. CheMin has returned quantitative mineral abundances from 16 mudstone, sandstone, and aeolian sand samples so far. The mineralogy of these samples is incredibly diverse, suggesting a variety of depositional and diagenetic environments and different source regions for the sediments. Results from CheMin have been essential for reconstructing the geologic history of Gale crater and addressing the question of habitability on ancient Mars.

Rampe, E. B.↗
NASA NTRS2017

Mineralogical Results from the Mars Science Laboratory Rover Curiosity

NASA's CheMin instrument, the first X-ray Diffractometer flown in space, has been operating on Mars for nearly five years. CheMin was first to establish the quantitative mineralogy of the Mars global soil (1). The instrument was next used to determine the mineralogy of a 3.7 billion year old lacustrine mudstone, a result that, together with findings from other instruments on the MSL Curiosity rover, documented the first habitable environment found on another planet (2). The mineralogy of this mudstone from an ancient playa lake was also used to derive the maximum concentration of CO2 in the early Mars atmosphere, a surprisingly low value that calls into question the current theory that CO2 greenhouse warming was responsible for the warm and wet environment of early Mars. CheMin later identified the mineral tridymite, indicative of silica-rich volcanism, in mudstones of the Murray formation on Mt. Sharp. This discovery challenges the paradigm of Mars as a basaltic planet and ushers in a new chapter of comparative terrestrial planetology (3). CheMin is now being used to systematically sample the sedimentary layers that comprise the lower strata of Mt. Sharp, a 5,000 meter sequence of sedimentary rock laid down in what was once a crater lake, characterizing isochemical sediments that through their changing mineralogy, document the oxidation and drying out of the Mars in early Hesperian time.

Mars mineralogy↗
NASA NTRS2017

Measuring N2 Pressure Using Cyanobacteria Discipline: Geomicrobiology

The evolution of Earth's atmosphere has been governed by biological evolution. Dinitrogen (N2) has been a major constituent of Earth's atmosphere throughout the planet's history, yet only a few constraints exist for the partial pressure of N2 (pN2). In this study we evaluate two new potential proxies for pN2: the physical spacing between heterocysts and the isotopic signature of nitrogen fixation in filamentous cyanobacteria. Heterocyst-forming filamentous cyanobacteria are some of the oldest photosynthetic microorganisms on Earth, and debated fossilized specimens have been found in sedimentary rocks as old as 2 Ga. These organisms overcome nitrogen limitation in their aqueous environment through cellular differentiation along their filaments. The specialized cells that develop, known as heterocysts, fix the nitrogen and laterally distribute it to neighboring cells along the filaments. Because the concentration of the dissolved N2 available to the filaments correlates directly with pN2, any preservable physiological response of the organism to the changed N2 availability constitutes a potential proxy for pN2. In the laboratory, we have examined how pN2 is reflected in the heterocyst spacing pattern and in the isotopic signature of nitrogen fixation by subjecting the representative species Anabaena cylindrica and Anabaena variabilis to different N2 partial pressures during growth at constant temperature and lighting (in media free of combined nitrogen). We show experimentally that the distance between heterocysts and the nitrogen isotope fractionation measured in bulk biomass reflect the pN2 experienced by Anabaena cylindrica. Current work is investigating these responses in Anabaena variabilis. When heterocystous cyanobacteria fossilize, these morphological and isotopic signatures should preserve information about pN2 at that time. Application of this relationship to the rock record may provide a paleoproxy to complement the two existing geobarometers.

nitrogen↗
NASA NTRS2016

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Miller, Kristen E.↗