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NASA NTRS2012

Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.

Graff, Trevor G.↗
NASA NTRS2012

Sporadic Groundwater Upwelling in Deep Martian Craters: Evidence for Lacustrine Clays and Carbonates

While the surface of Mars may have had an active hydrosphere early in its history [1], it is likely that this water retreated to the subsurface early on due to loss of the magnetic field and early atmosphere [2]. This likely resulted in the formation of two distinct aqueous regimes for Mars from the Late Noachian onward: one dominated by redistribution of surface ice and occasional melting of snow/ice [3], and one dominated by groundwater activity [4]. The excavation of alteration minerals from deep in the crust by impact craters points to an active, ancient, deep hydrothermal system [5]. Putative sapping features [6] may occur where the groundwater breached the surface. Upwelling groundwater may also have played a critical role in the formation of massive, layered, cemented sediments in Sinus Meridiani [7,8], in the Valles Marineris [9], and possibly in Gale Crater [10], where the Curiosity Rover will land later this year. Understanding the past distribution, geochemistry, and significance of groundwater on Mars is critical to untangling the origins of deep alteration minerals, Hesperian sulfate deposits, and crater fill deposits at Gale Crater or in other locations.

Michalski, J. R.↗
NASA NTRS2012

The Search for Life on Mars

For centuries, the planet Mars has been regarded as a possible abode for life. Serious searches for the signatures of life began in the 19th century, and continue via telescopic investigations and landed missions. While early work focused on phenomenology and bordered on fantasy, modern scientific inquiry has emphasized the search for chemical signatures of life in the soil and rocks at the planet's surface, and the search for biomarker gases in the atmosphere. Living systems produce more than 90% of Earth's atmospheric methane; the balance is of geochemical origin. The discovery of methane on Mars will be described, along with the ongoing extended search for clues to its origins. The possible origins of Mars methane will be discussed in the context of terrestrial analogue sites where geologic and biologic methane production now occurs - ranging from sub-permafrost zones in the arctic to hydrothermal vents in the deep ocean. Terrestrial organisms that could prosper on Mars today will be mentioned. I will briefly touch upon experiments conducted by landed spacecraft, ranging from the Viking Life Science Experiments in 1976 to the impending Mars Science laboratory, and the Trace Gas Orbiter and ExoMars missions now being developed for flight in the coming decade.

Mumma, Michael J.↗
NASA NTRS2012

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Socki, Richard A.↗
NASA NTRS2010

Iron Homeostasis in Yellowstone National Park Hot Spring Microbial Communities

It has been postulated that life may have originated on Earth, and possibly on Mars, in association with hydrothermal activity and high concentrations of ferrous iron. However, it is not clear how an iron-rich thermal hydrosphere could be hospitable to microbes, since reduced iron appears to stimulate oxidative stress in all domains of life and particularly in oxygenic phototrophs. Therefore, the study of microbial diversity in iron-depositing hot springs (IDHS) and the mechanisms of iron homeostasis and suppression of oxidative stress may help elucidate how Precambrian organisms could withstand the extremely high concentrations of reactive oxygen species (ROS) produced by interaction between environmental Fe(2+) and O2. Proteins and clusters of orthologous groups (COGs) involved in the maintenance of Fe homeostasis found in cyanobacteria (CB) inhabiting environments with high and low [Fe] were main target of this analysis. Preliminary results of the analysis suggest that the Chocolate Pots (CP) microbial community is heavily dominated by phototrophs from the cyanobacteria (CB), Chloroflexi and Chlorobi phyla, while the Mushroom Spring (MS) effluent channel harbors a more diverse community in which Chloroflexi are the dominant phototrophs. It is speculated that CB inhabiting IDHS have an increased tolerance to both high concentrations of Fe(2+) and ROS produced in the Fenton reaction. This hypothesis was explored via a comparative analysis of the diversity of proteins and COGs involved in Fe and redox homeostasis in the CP and MS microbiomes.

Brown, I.↗
NASA NTRS2012

A "Warm Formamide" Scenario for the Origins of Life Might not be so Hot: Comment on "Formamide and the Origin of Life"

In this review, Saladino et al. present an intriguing hypothesis surrounding the role of formamide in the origins of life on Earth, backed by experimental results supporting each step from formamide to RNA polymers. The overall premise is that, from formamide and inorganic phosphate, RNA molecules over 100 nucleotides in length can be produced. In addition, many carboxylic acids likely relevant to prebiotic metabolism, are formed along the way. Thus, from a rather simple organic molecule that has been observed in outer space (formamide), you can generate many of the compounds necessary for the origins of life. However, because high temperatures (160 C) are required for the formamide reactions, it remains unclear where the "warm formamide" scenario could have occurred. Low-temperature, aqueous hydrogen cyanide-based prebiotic chemistry that we know actually happened has been shown to produce many of the molecules invoked in the formamide hypothesis: amino acids, carboxylic acids, sugar acids, and nucleobases have all been found in meteorites recovered on Earth, providing a plausible route for their synthesis and delivery. In contrast, a large portion of the formamide hypothesis is based on relatively hightemperature reactions, A plausible milieu for high-temperature reactions with concentrated formamide is yet to be described, and is critical for this hypothesis to be validated. Hydrothermal vents are attractive heat sources, and the higher boiling point of formamide has been invoked as a mechanism to concentrate it from an aqueous solution, Unless the water can actually evaporate, however, there would be no net enrichment. For example, in the context of a deep-sea vent, any water "removed" by heating would be quickly replaced. Some of the individual reactions underpinning the present hypothesis have been met with skepticism because they go against conventional wisdom, To name a few of the surprising results: the observation that nucleosides can be converted to cyclic phosphates when heated in the presence of minerals and inorganie phosphate; that 3'-5' cGMP and cAMP nucleotides polymerize rapidly into RNA oligomers, even in the absence of monovalent counterions and that end-to-end ligation reactions between RNA oligomers occur in essentially pure water, without requiring any activating groups or counterions. Because the polymerization reactions are simply transesterification reactions, that they readily occur in the absence of cations makes one wonder why nearly all ribozyme-catalyzed transesterification reactions are metal-ion dependent; similarly, that the end-to-end ligation reactions do not require activation runs counter to the observation that all protein-catalyzed ligation and polymerization reactions of RNA and DNA require activated substrates. Detailed mechanistic studies of the reported reactions are warranted and could provide important insights for understanding the chemistry behind the origins of life. Because the authors have produced many of the experimental results supporting their hypothesis, they could demonstrate the validity of their hypothesis by converting formamide into approx 100 nucleotide RNA oligomers, using the products of one reaction as the reactants for the next reaction, under specific conditions plausible on the pre-biotic Earth. Such a demonstration would represent a milestone for our understanding of the origins of life.

Burton, Aaron S.↗
NASA NTRS2012

Multiple Smaller Missions as a Direct Pathway to Mars Sample Return

Recent discoveries by the Mars Exploration Rovers, Mars Express, Mars Odyssey, and Mars Reconnaissance Orbiter spacecraft include multiple, tantalizing astrobiological targets representing both past and present environments on Mars. The most desirable path to Mars Sample Return (MSR) would be to collect and return samples from that site which provides the clearest examples of the variety of rock types considered a high priority for sample return (pristine igneous, sedimentary, and hydrothermal). Here we propose an MSR architecture in which the next steps (potentially launched in 2018) would entail a series of smaller missions, including caching, to multiple landing sites to verify the presence of high priority sample return targets through in situ analyses. This alternative architecture to one flagship-class sample caching mission to a single site would preserve a direct path to MSR as stipulated by the Planetary Decadal Survey, while permitting investigation of diverse deposit types and providing comparison of the site of returned samples to other aqueous environments on early Mars

Niles, P. B.↗
NASA NTRS2012

Nitrogen Isotopic Composition of Organic Matter in a Pristine Collection IDP

Anhydrous chondritic porous interplanetary dust particles (CP IDPs) are probable cometary materials that show primitive characteristics, such as unequilibrated mineralogy, fragile structure, and abundant presolar grains and organic matter [1-3]. CP IDPs are richer in aliphatic species and N-bearing aromatic hydrocarbons than meteoritic organics and commonly exhibit highly anomalous H and N isotopic compositions [4,5]. Cometary organic matter is of interest in part because it has escaped the hydrothermal processing experienced by meteorites. However, IDPs are collected using silicon oil that must be removed with strong organic solvents such as hexane. This procedure is likely to have removed some fraction of soluble organic phases in IDPs. We recently reported the first stratospheric collection of IDPs without the use of silicone oil [6]. Here we present initial studies of the carbonaceous material in an IDP from this collection.

Messenger, S.↗
NASA NTRS2012

Appropriate Simulants are a Requirement for Mars Surface Systems Technology Development

To date, there are two simulants for martian regolith: JSC Mars-1A, produced from palagonitic (weathered) basaltic tephra mined from the Pu'u Nene cinder cone in Hawaii [1] by commercial company Orbitec, and Mojave Mars Simulant (MMS), produced from Saddleback Basalt in the western Mojave desert by the Jet Propulsion Laboratory [2]. Until numerous recent orbiters, rovers, and landers were sent to Mars, weathered basalt was surmised to cover every inch of the martian landscape. All missions since Viking have disproven that the entire martian surface is weathered basalt. In fact, the outcrops, features, and surfaces that are significantly different from weathered basalt are too numerous to realistically count. There are gullies, evaporites, sand dunes, lake deposits, hydrothermal deposits, alluvium, etc. that indicate sedimentary and chemical processes. There is no one size fits all simulant. Each unique area requires its own simulant in order to test technologies and hardware, thereby reducing risk.

Edmunson, Jennifer E.↗
NASA NTRS2013

The Gale Crater Mound in a Regional Geologic Setting: Mapping and Probing Surrounding Outcrops for Areas Akin to the Central Mound at Gale

There are several hypotheses on the origin of Gale Crater s central mound. These include ground water upwelling [1], aeolian, ice, volcanic [1-3], lacustrine [1-3], hydrothermal [1-3], and polar deposits [2]. The Mars Science Laboratory rover, Curiosity, landed in Gale Crater on August 6, 2012. It is currently analyzing samples along its traverse towards a channel and layered deposits that will provide insight into the sedimentary history of the crater [4]. Located at 5S, 138E, Gale is a 155km diameter, Late Noachian/Early Hesperian crater. It is situated along the southern highlands/northern lowlands dichotomy boundary and contains a central mound that rises approximately 5km from the crater floor [1]. The highest parts of Mt. Sharp are higher than the northern rim, but are roughly the same height as the southern rim. Mt. Sharp is divided into an upper mound and a lower mound, which are separated by an erosional unconformity [2]. The lower mound s sequences span the Late Noachian/Early Hesperian Epoch [1], while the upper mound s age is poorly constrained. The lower mound s sequences feature parallel beds of varying thickness, albedo, texture, and dip angle that are eroded into channels and yardangs [2]. The upper mound has finer layers at higher angles [1] with yardangs, serrated erosional patterns, and lobate features [3]. The lower mound also exhibits an upward progression of phyllosilicate to sulfate rich sediments, contrasting the upper mound s lack of hydrated minerals [4].

Korn, Lisa↗
NASA NTRS2012

Microbial Lipid and C Isotopic Biosignatures of a Unique Community at Grand Prismatic Spring, Yellowstone National Park

The microbial communities found in modern hot springs are considered analogs to ones that may have existed in hydrothermal systems on the early Earth and possibly Mars. Our goal was to characterize the microbial biosignatures and to assess the preservation of organic matter in the silica-depositing Grand Prismatic Spring in Yellowstone National Park. This study combines 16S rRNA surveys, lipid biomarkers, and C isotopes to query, "Who's there and what are they doing?" On the edge of the approximately 90 m diameter blue vent pool (56.1 C, pH 8.5), a floating green streamer community grew over a benthic pink community. The membrane lipids in the green streamers and pink mat were composed of unusual ester-linked fatty acids, indicating the presence of novel bacterial groups. In particular, we discovered a series of 2-methyl and 2,X-dimethyl phospholipid fatty acids (C18-22). We are attempting to use the 16S rRNA surveys to link these compounds to source organisms. Wax esters, biomarkers for Chloroflexi, were present in both communities, but displayed different profiles. A higher proportion of branched wax esters were found in the green streamers, and were associated with a relatively high concentration of long-chain di- and trienes (C29-31). This suggests that Chloroflexus primarily grew in the green streamers, while a pink mat of Roseiflexus grew on the sinter substrate underneath. Cyanobacterial alkanes were found in the green streamers (n-C17, 7-, 6- and 5-monomethyl-C17, 7,11-dimethyl-C17, n-C19, n-C19:1). We also detected a series of monoalkylglycerylethers and geologically relevant hopanoids in both communities. Carbon isotope analyses indicated that Chloroflexus was growing photoheterotrophically using cyanobacterial photosynthate. Roseiflexus also traditionally grows photoheterotrophically, but the C isotopic signatures of the lipids in the pink mat were approximately 10 %0 lighter than the cyanobacterial and Chloroflexus lipids, indicating a potentially novel metabolic mechanism or prior secondary reworking of substrates before reaching Roseiflexus. This arrangement of Synechococcus-Chloroflexus green streamers floating over a benthic pink community of Roseiflexus is different from the classical laminated Synechococcus-Chloroflexi mats at Octopus Hot Spring.

Jahnke, Linda↗
NASA NTRS2012

Initial Observations by the Mars Exploration Rover Opportunity at Cape York, Meridiani Planum

Since the beginning of its mission, the MER rover Opportunity has visited a sequence of progressively larger impact craters in order to characterize rocks that represent an ever broader stratigraphic range. Endeavour Crater is by far the largest crater that this rover has visited, therefore the crater rim provides materials from strata that are much deeper and older than any materials yet sampled. Indeed, the Mars Reconnaissance Orbiter CRISM instrument detected spectral signatures of hydrated phyllosilicates in several rim segments, consistent with a Noachian provenance. In addition, the crater rim might have recorded the effects of the original impact as well as the thermal processes that occurred in its aftermath. This report summarizes initial observations of geologic structures and the fabrics, chemistry and mineralogy of rocks. Cape York is an N/NE - S/SW-trending segment of crater rim that is bounded by rim segments that are more deeply eroded, forming embayments. Opportunity drove onto the southwest margin of Cape York and has traversed across the Cape to a ridge near its northern end. The rim of Endeavour Crater was severely degraded and then on lapped by Meridiani sulfate-rich deposits, indicating that Cape York deposits experienced extensive erosion prior to the deposition of Meridiani Planum sulfate-rich sediments. Cape York consists of impact-uplifted rocks that are surrounded by a younger bedrock bench that might represent sediments shed from Cape York. The uplifted rock "Tisdale-2," located near the southern end of Cape York, is a polymict lithic breccia. Its elemental composition resembles a mixture of basalt plus bedrock encountered previously at Meridiani Planum, and it is relatively enriched in Ni, Zn, P, characteristic of hydrothermal fluids. "Chester Lake" and "Greeley Haven" are bedrock surfaces located near the southern and northern ends of Cape York, respectively, and they exhibit fabrics reminiscent of suevites. The rocks that were analyzed so far are quite different from any rocks previously encountered by Opportunity and Spirit. Several light-toned vein deposits (approx 1 cm) were discovered in the bench that borders the western flanks of Cape York. The vein "Homestake" is rich in Ca and S, and it exhibits a spectral feature near 1000 run caused by hydration, indicating that "Homestake" consists substantially of gypsum. The relationship(s) between these veins and the sulfate-rich layered deposits at Meridiani Planum remains uncertain. The veins might have been deposited by sulfate-rich fluids perhaps either in the immediate aftermath of the impact that formed Endeavour Crater or at some later time. Current uncertainties notwithstanding, the novel lithologies at Cape York are significantly older than the sulfate-rich sedimentary rocks at Meridiani Planum, and these lithologies have recorded episodes of aqueous activity from earlier epochs, perhaps during the Noachian. The author acknowledges the contributions of the Athena Science Team, the MER engineering team, JPL and NASA.

Marais, David J.↗
NASA NTRS2013

Reflectance Spectra Diversity of Silica-Rich Materials: Sensitivity to Environment and Implications for Detections on Mars

Hydrated silica-rich materials have recently been discovered on the surface of Mars by the Mars Exploration Rover (MER) Spirit, the Mars Reconnaissance Orbiter (MRO) Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), and the Mars Express Observatoire pour la Mineralogie, l'Eau, les Glaces, et l'Activite'(OMEGA) in several locations. Having been interpreted as hydrothermal deposits and aqueous alteration products, these materials have important implications for the history of water on the martian surface. Spectral detections of these materials in visible to near infrared (Vis NIR) wavelengths have been based on a H2O absorption feature in the 934-1009 nm region seen with Spirit s Pancam instrument, and on SiOH absorption features in the 2.21-2.26 micron range seen with CRISM. Our work aims to determine how the spectral reflectance properties of silica-rich materials in Vis NIR wavelengths vary as a function of environmental conditions and formation. Here we present laboratory reflectance spectra of a diverse suite of silica-rich materials (chert, opal, quartz, natural sinters and synthetic silica) under a range of grain sizes and temperature, pressure, and humidity conditions. We find that the H2O content and form of H2O/OH present in silica-rich materials can have significant effects on their Vis NIR spectra. Our main findings are that the position of the approx.1.4 microns OH feature and the symmetry of the approx.1.9 microns feature can be used to discern between various forms of silica-rich materials, and that the ratio of the approx.2.2 microns (SiOH) and approx.1.9 microns (H2O) band depths can aid in distinguishing between silica phases (opal-A vs. opal-CT) and formation conditions (low vs. high temperature). In a case study of hydrated silica outcrops in Valles Marineris, we show that careful application of a modified version of these spectral parameters to orbital near-infrared spectra (e.g., from CRISM and OMEGA) can aid in characterizing the compositional diversity of silica-bearing deposits on Mars. We also discuss how these results can aid in the interpretation of silica detections on Mars made by the MER Panoramic Camera (Pancam) and Mars Science Laboratory (MSL) Mast-mounted Camera (Mastcam) instruments.

Rice, M. S.↗
NASA NTRS2013

A Mars Sample Return Sample Handling System

We present a sample handling system, a subsystem of the proposed Dragon landed Mars Sample Return (MSR) mission [1], that can return to Earth orbit a significant mass of frozen Mars samples potentially consisting of: rock cores, subsurface drilled rock and ice cuttings, pebble sized rocks, and soil scoops. The sample collection, storage, retrieval and packaging assumptions and concepts in this study are applicable for the NASA's MPPG MSR mission architecture options [2]. Our study assumes a predecessor rover mission collects samples for return to Earth to address questions on: past life, climate change, water history, age dating, understanding Mars interior evolution [3], and, human safety and in-situ resource utilization. Hence the rover will have "integrated priorities for rock sampling" [3] that cover collection of subaqueous or hydrothermal sediments, low-temperature fluidaltered rocks, unaltered igneous rocks, regolith and atmosphere samples. Samples could include: drilled rock cores, alluvial and fluvial deposits, subsurface ice and soils, clays, sulfates, salts including perchlorates, aeolian deposits, and concretions. Thus samples will have a broad range of bulk densities, and require for Earth based analysis where practical: in-situ characterization, management of degradation such as perchlorate deliquescence and volatile release, and contamination management. We propose to adopt a sample container with a set of cups each with a sample from a specific location. We considered two sample cups sizes: (1) a small cup sized for samples matching those submitted to in-situ characterization instruments, and, (2) a larger cup for 100 mm rock cores [4] and pebble sized rocks, thus providing diverse samples and optimizing the MSR sample mass payload fraction for a given payload volume. We minimize sample degradation by keeping them frozen in the MSR payload sample canister using Peltier chip cooling. The cups are sealed by interference fitted heat activated memory alloy caps [5] if the heating does not affect the sample, or by crimping caps similar to bottle capping. We prefer cap sealing surfaces be external to the cup rim to prevent sample dust inside the cups interfering with sealing, or, contamination of the sample by Teflon seal elements (if adopted). Finally the sample collection rover, or a Fetch rover, selects cups with best choice samples and loads them into a sample tray, before delivering it to the Earth Return Vehicle (ERV) in the MSR Dragon capsule as described in [1] (Fig 1). This ensures best use of the MSR payload mass allowance. A 3 meter long jointed robot arm is extended from the Dragon capsule's crew hatch, retrieves the sample tray and inserts it into the sample canister payload located on the ERV stage. The robot arm has capacity to obtain grab samples in the event of a rover failure. The sample canister has a robot arm capture casting to enable capture by crewed or robot spacecraft when it returns to Earth orbit

Wilson, David↗
NASA NTRS2012

A 'Warm Formamide' Scenario for the Origins of Life Might Not Be so Hot Comment on 'Formamide and the Origin of Life' by E. Di Mauro Et Al.

In this review, Saladino et al. present an intriguing hypothesis surrounding the role of formamide in the originsof life on Earth, backed by experimental results supporting each step from formamide to RNA polymers [1]. The overall premise is that, from formamide and inorganic phosphate, RNA molecules over 100 nucleotides in length canbe produced. In addition, many carboxylic acids likely relevant to prebiotic metabolism are formed along the way. Thus, from a rather simple organic molecule that has been observed in outer space (formamide), you can generatemany of the compounds necessary for the origins of life. However, because high temperatures (160 C) are requiredfor the formamide reactions, it remains unclear where the warm formamide scenario could have occurred.Low-temperature, aqueous hydrogen counter to the observation that all protein-catalyzed ligation and polymerization reactions of RNA and DNA requireactivated substrates. Detailed mechanistic studies of the reported reactions are warranted and could provide important insights for understanding the chemistry behind the origins of life.Because the authors have produced many of the experimental results supporting their hypothesis, they coulddemonstrate the validity of their hypothesis by converting formamide into 100 nucleotide RNA oligomers, usingthe products of one reaction as the reactants for the next reaction, under specific conditions plausible on the pre-bioticEarth. Such a demonstration would represent a milestone for our understanding of the origins of life.cyanide-based prebiotic chemistry that we know actually happened has beenshown to produce many of the molecules invoked in the formamide hypothesis: amino acids, carboxylic acids, sugaracids, and nucleobases have all been found in meteorites recovered on Earth [e.g. [24]], providing a plausible routefor their synthesis and delivery. In contrast, a large portion of the formamide hypothesis is based on relatively high-temperature reactions. A plausible milieu for high-temperature reactions with concentrated formamide is yet to bedescribed, and is critical for this hypothesis to be validated. Hydrothermal vents are attractive heat sources, and the higher boiling point of formamide has been invoked as a mechanism to concentrate it from an aqueous solution.Unless the water can actually evaporate, however, there would be no net enrichment. For example, in the context of a deep-sea vent, any water removed by heating would be quickly replaced.Some of the individual reactions underpinning the present hypothesis [1] have been met with skepticism becausethey go against conventional wisdom. To name a few of the surprising results: the observation that nucleosides can beconverted to cyclic phosphates when heated in the presence of minerals and inorganic phosphate [5]; that 35 cGMPand cAMP nucleotides polymerize rapidly into RNA oligomers, even in the absence of monovalent counterions [6];and that end-to-end ligation reactions between RNA oligomers occur in essentially pure water, without requiring any activating groups or counterions [7,8]. Because the polymerization reactions are simply transesterification reactions,that they readily occur in the absence of cations makes one wonder why nearly all ribozyme-catalyzed transesterification reactions are metal-ion dependent; similarly, that the end-to-end ligation reactions do not require activation runs.

life↗
NASA NTRS2014

Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Peretyazhko, Tanya↗
NASA NTRS2014

Experimental Alteration of Basalt to Support Interpretation of Remote Sensing and In Situ Meausrements from Mars

Major occurrences of hydrous alteration minerals on Mars have been found in Noachian impact craters formed in basaltic targets and detected using visible/near infrared (VNIR) spectroscopy. Until recently phyllosilicates were detected only in craters in the southern hemisphere [1, 2]. However, it has been reported that at least nine craters in the northern plains apparently excavated thick layers of lava and sediment to expose phyllosilicates [3] as well. The MER (Mars Exploration Rovers) rovers previously reported results of in situ measurement indicating the presence of alteration minerals on Mars [4,5] and it was recently reported that the Mars Curiosity rover has detected alteration phases in situ at Yellowknife Bay in Gale crater as well [6,7]. An important discovery for Mars geochronology is that the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument on Curiosity detected phyllosilicates indicating that phyllosilicate formation on Mars extended beyond the Noachian Epoch [8]. These discoveries indicate that Mars was globally altered by water in the past but does not constrain formation conditions for alteration phase occurrences, which have important implications for the evolution of the surface and the biological potential on Mars. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures as well as in situ measurements and to decipher the environment and evolution of early Mars. The martian surface has been intensely altered by meteorite impacts whose effects include brecciation and melting of target materials as well as the initiation of hydrothermal circulation in a hydrous target [9,10,11,12]. Impact effects may facilitate aqueous alteration of a basaltic target because the rate of silicate dissolution is a function of the degree of crystallinity, surface area, and temperature. The resultant alteration mineralogies from shocked basaltic target material are a function of the original mineral assemblage in the parent rocks, the chemistry of fluids that interacted with the rocks, and physico-chemical conditions (pH, temperatures, and pressure) during the time of mineral formation. Understanding the alteration assemblages produced by a range of conditions is vital for the interpretation of phyllosilicate spectral signatures and to decipher the environment and evolution of early Mars, and especially for identifying habitable niches in which life could be initiated and sustained. No experimentally controlled and well characterized analog materials that simulate martian shock metamorphism and alteration conditions currently exist for calibrating either remote sensing or in situ measurements of Mars. A series of experiments was initiated to assess the effects of systematic changes in the physico-chemical conditions on Mars analog materials thereby providing samples to ground-truth Mars remote sensing observations from CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) and in situ measurements from Opportunity's Mössbauer and Curiosity's CHEMIN (Chemistry and Mineralogy X-Ray Diffraction/XRay Fluorescence) instruments. Results of initial experimental runs as analysed by SEM-EDS (Secondary Electron Microscopy -Energy Dispersive Spectroscopy) and X-ray Diffraction (XRD) analysis are reported here and lay the foundation for comparison with shocked and altered samples that will be characterized in the next phase of this work.

Bell, M. S.↗
NASA NTRS2014

Exploring Mars for Evidence of Habitable Environments and Life

The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising candidates. The Mars Exploration Rover (MER) Opportunity revealed that water once flowed to the surface across the vast Meridiani plains, creating saline lakes whose waters were roiled by ancient winds that also sculptured their salt deposits into sand dunes. Opportunity then drove more than 30 km to explore even older deposits on a crater rim. MER Spirit found evidence that thermal waters (heated by volcanism or by impacts?) altered rocks to create sulfate salts, and siliceous sinters. These discoveries indicate that an early hydrological cycle apparently sustained precipitation, streams and lakes. Liquid water participated in rock weathering reactions, such as iron and sulfur oxidation, that created distinctive weathering regimes. Volcanism, impacts, groundwater and ice interacted at least locally. Redox chemical energy from volcanism, hydrothermal activity and weathering of crustal materials would have been available for any life. Thus conditions might have supported life in the past, at least locally. The main objective of the Mars Science Laboratory (MSL) Curiosity rover is to determine the extent to which Gale crater hosted environments capable of supporting microbial life. The rover has already found stream gravels as well as sediments that might have been deposited in an ancient lake. The rover is now traversing to Mt. Sharp, a 5 km-high mound that is located on the crater floor and that exhibits layered sedimentary rocks having diverse minerals (sulfates and clays) that apparently formed in the presence of liquid water. This rock sequence was deposited over an extended time period in diverse potentially habitable watery environments. Curiosity is poised to characterize a a well-preserved rock record of hundreds of millions of years of diverse environments and profound climate change.

layered phyllosilicates↗