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NASA NTRS2011

A Terrestrial Analogue from Spitsbergen (Svalbard, Norway) for the Comanche Carbonate at Gusev Crater, Mars

Carbonate occurs at the Comanche outcrops in Gusev Crater on the basis of analyses made by the Mars Exploration Rover Spirit [1]. Taken together, mineralogical data from Spirit's Moessbauer (MB) and Mini-TES spectrometer and chemical data from the APXS spectrometer show that Comanche carbonate has an Mg-Fe-rich bulk chemical composition, is present at high concentrations, and is distributed throughout the outcrop and not just at the MB and APXS analysis location. The granular outcrop texture and the observation that it appears to be resistant to weathering compared with surrounding material [1] imply that the carbonate may be present as a cement. A hydrothermal origin for the Comanche carbonate was inferred by analogy with laboratory experiments and with a carbonate occurrence within the Bockfjord volcanic complex on the island Spitsbergen (Svalbard, Norway) [1]. The laboratory carbonates, synthesized by precipitation from hydrothermal solutions, have (MB) parameters and average bulk chemical compositions that are characteristic of Comanche carbonate. The connection to Comanche carbonate is only through chemical data for certain occurrences of Spitsbergen carbonates. In fact, the common average bulk chemical composition for these Spitsbergen carbonates, the synthetic carbonates, the Comanche carbonate, and also the carbonate globules found in martian meteorite ALH84001 is a chemical constraint consistent with a hydrothermal formation process for all the carbonates [e.g., 1-3]. We develop here a link between MB data for the Comanche carbonate from MER and MB data for certain Spitsbergen carbonate occurrences from laboratory measurements. We also obtained visible and near- IR spectra on Spitsbergen carbonates for comparison with martian carbonate detections made on the basis of CRISM spectral data, e.g., in Nili Fossae [4].

Morris, Richard V.↗

NASA NTRS2000

Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry

Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx. 600 C experienced by ALH84001. Here, we report thermal and compositional characterization of unshocked siderite and its transition to magnetite. Additional information is contained in the original extended abstract.

Bell, M. S.↗

NASA NTRS2011

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

Fu, Qi↗

NASA NTRS1984

Carbon and its isotopes in mid-oceanic basaltic glasses

Sample surface carbon, mantle carbon dioxide in vesicles, and mantle carbon dissolved in glasses, are the three carbon components evident in the 11 mid-oceanic basalts presently analyzed. The total carbon content may be controlled by the depth of the shallowest ridge magma chamber, and carbon isotopic fractionation accompanies magma degassing. Using He-3 and carbon data for submarine hydrothermal fluids, the present day midoceanic ridge carbon flux is approximately estimated to be 1.0 x 10 to the 13th g C/yr, requiring 8 Gyr to accumulate the earth's present crustal carbon inventory.

Des Marais, D. J.↗

NASA NTRS2011

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Socki, Richard A.↗

NASA NTRS2020

The Old, Unique C1 Chondrite Flensburg – Insight Into the First Processes of Aqueous Alteration, Brecciation, and the Diversity of Water-Bearing Parent Bodies and Lithologies

On September 12, 2019 at 12:49:48 (UT) a bolide was observed by hundreds of eye-witnesses from the Netherlands, Germany, Belgium, Denmark and the UK. One day later a small meteorite stone was found by accident in Flensburg. The presence of short-lived cosmogenic radionuclides with half-lives as short as 16 days proves the recent exposure of the found object to cosmic rays in space linking it clearly to the bolide event. An exceptionally short exposure time of ∼5000 years was determined. The 24.5 g stone has a fresh black fusion crust, a low density of <2 g/cm(exp 3), and a magnetic susceptibility of logχ = 4.35 (χ in 10−9 m(exp 3)/kg). The rock consists of relict chondrules and clusters of sulfide and magnetite grains set in a fine-grained matrix. The most abundant phases are phyllosilicates. Carbonates (∼3.9 vol.%) occur as calcites, dolomites, and a Na-rich phase. The relict chondrules (often surrounded by sulfide laths) are free of anhydrous silicates and contain abundant serpentine. Lithic clasts are also surrounded by similar sulfide laths partly intergrown with carbonates. Mn-53-Cr-53 ages of carbonates in Flensburg indicate that brecciation and contemporaneous formation of the pyrrhotite-carbonate intergrowths by hydrothermal activities occurred no later than 4564.6 ± 1.0 Ma (using the angrite D'Orbigny as the Mn-Cr age anchor). This corresponds to 2.6 ± 1.0 or 3.4 ± 1.0 Ma after formation of CAIs, depending on the exact absolute age of CAIs. This is the oldest dated evidence for brecciation and carbonate formation, which likely occurred during parent body growth and incipient heating due to decay of Al-26. In the three oxygen isotope diagram, Flensburg plots at the 16O-rich end of the CM chondrite field and in the transition field to CV-CK-CR chondrites. The mass-dependent Te isotopic composition of Flensburg is slightly different from mean CM chondrites and is most similar to those of the ungrouped C2 chondrite Tagish Lake. On the other hand, Ti-50 and Cr-54 isotope anomalies indicate that Flensburg is similar to CM chondrites, as do the ∼10 wt.% H2O of the bulk material. Yet, the bulk Zn, Cu, and Pb concentrations are about 30% lower than those of mean CM chondrites. The He, Ne, and Ar isotopes of Flensburg show no solar wind contribution; its trapped noble gas signature is similar to that of CMs with a slightly lower concentration of Ne(sub tr)-20. Based on the bulk H, C, and N elemental abundances and isotopic compositions, Flensburg is unique among chondrites, because it has the lightest bulk H and N isotopic compositions of any type 1 or 2 chondrite investigated so far. Moreover, the number of soluble organic compounds in Flensburg is even lower than that of the brecciated CI chondrite Orgueil. The extraordinary significance of Flensburg is evident from the observation that it represents the oldest chondrite sample in which the contemporaneous episodes of aqueous alteration and brecciation have been preserved. The characterization of a large variety of carbonaceous chondrites with different alteration histories is important for interpreting returned samples from the OSIRIS-REx and Hayabusa 2 missions.

C1 chondrite↗

NASA NTRS1998

Ma'adim Vallis Estuarine Delta in Elysium Basin and Its Relevance as a Landing Site for Exobiology Exploration on Mars

The debouche of Ma'adim Vallis in the Elysium Basin generated a transitional transported sediment structure, which planimetric shape is controlled by the enclosing topography of a deep reentrant gulf of the Basin into the highland. We defined it as an estuarine delta. The location and the importance of this estuarine delta is supported by the theoretical model of graded profile constructed for Ma'adim Vallis, and by two approaches: (i) the reconstruction of Ma'adim Vallis downstream course from Gusev to Elysium Basin, and (ii) the survey of the sediment deposit in the alleged estuary. The longitudinal graded profile of Ma'adim Vallis finds its base-level in the Elysium Basin, at a about 1000 m elevation, which is in agreement with the observed Basin shoreline. This model is supported by observational evidence of flow between the northern rim of Gusev crater, and the Elysium Basin shoreline. This downstream course of Ma'adim Vallis can be divided into three hydrogeologic regions. into three hydrogeologic regions. (a) The first region is a flooded plain (Zephiria Mensae), consisting in chaotic terrain formed by highland rocks, and disintegrated lava of the western flank of Apollinaris. Morphologic indicators of the flood process are: (1) the sediment deposit over the Gusev crater northern rim that reflects the overspilling of the crater-lake water through a 40-km wide gap provided by an ancient impact crater, (2) the tear-drop shaped feature on the northeastern flank of Apollinaris Patera, and (3) the chaotic terrain that suggest the emergence of ground water generated by the seepage of the crater lake through high-permeable broken rampart material. This underground water circulation sustained by the hydrostatic pressure of the crater-lake has likely generated a hydrothermal system in the volcanic environment of Apollinaris Patera. The stratigraphy of the flooded area is identified as Hesperian age, with occurrences of Noachian hilly individual features, and as Amazonian flooded plain and chaotic material, (b) The second region is located on the western flank of Apollinaris Patera. It is surrounded by relics of deep valleys that suggest a former downstream course of Ma'adim Vallis. The geologic setting of this region (Lucus Planum) is interpreted to be an Amazonian formation composed by the middle and lower members of the Medusae Formation., c) The third region corresponds to the convergence of the west and east branches of Ma'adirn Vallis into a deep re-entrant wide gulf that penetrates about 100 km into the highland. This topographic depression is delineated by the 1000 in elevation contour. This gulf has formed an estuarine configuration centered at 3S/190W within the Elysium Basin. This configuration has favored the formation of a estuarine sedimentary delta, because of topographically controlled lateral migration. This estuarine structure is strongly dominated by the incoming supply of Ma'adim Vallis fluvial sediment extracted from Zephiria Mensae and Lucus Planum. The obtuse-angle geometry of the estuary increases the sedimentation rate, which is higher than in the course of the channel. The sediment deposition process is governed by the estuarine water circulation. The inflowing loaded fluvial water enters the estuary as a bottom current, and mixes with the relatively less-loaded water of the receiving basin. When they mixed. the inflowing fluvial material, and the landward basin circulating water generate an accumulation of highly-diversified estuarine deposit stratification. This accumulation of material is mostly centered in the transitional zone of the delta. The sediment trapping efficiency of the estuary is function of the energy balance between the inflowing fluvial water, and the ingoing basin current. The submergence of the delta by the rising of the water-level increases the estuary water-depth, and consequently the sediment entrapment is favored. The locus of sediment accumulation moves landward in the zone of inflowing fluvial water. This results in the rising of the channel base-level, thus in the increase of the length of the longitudinal graded-profile. The sediment deposit facies of the zone A shows a generally smooth surface. The longitudinal deposit is bordered by alluvial terraces that reflect the variations of the channel level. The waning of the Elysium Basin caused the erosion of the Basin estuarine zone by small channels, this episode being characterized by dissected tear-drop shaped mesa-like morphologies in the delta. Our estuarine delta model predicts a lithostratigraphic depositional sequence associated with the water submergence and the transgression of Elysium Basin. The thickness of the estuarine sediment corresponds to the Elysium Basin levels changes relatively to the bed floor of the estuary, The depositional sequence of Ma'adim Vallis are described: (1) a pro-current filled region (A), where fluvial are longitudinally accumulated by the inflowing water, (2) inverse current from Elysium Basin (B), where fluvial and lacustrine sediments are accumulated, and (3) zone of current equilibrium (C), where the sediments are distributed as a shoreline at the boundary of the estuarine delta. The estuary sedimentology dynamics collects and keeps the record of the geologic unit material crossed by Ma'adim Vallis, and those of the lakebed deposit of Elysium Basin. The predicted mixed stratigraphic sequence from fluvial and lacustrine sediment makes this site an exceptional environment to concentrate potential multi-origin biologic records. We envision four possible strategies to explore this sedimentologic record: (1) longitudinal surface and subsurface traverses in region A to investigate outcrop levees, (2) exploration of the mesa walls in region B, (3) deep drilling hole lodging of the sequential deposits in the zones A and B, and (4) surface and subsurface exploration of the shoreline delta. The expected results for each of these strategies are: (1) in the deepest layers of region A are predicted frequent and abundant coarse material, sandy lenses lamination grading downward from sand to cobbles. Volcanic debris from the Noachian crustal Plateau unit material, hydrothermal altered rocks, carbonates, Hesperian and possibly Amazonian volcanic material, from Apollinaris Patera, altered rocks and carbonates from Zephiria Mensae are expected. As a favorable environment for inception of life, possible biological records are expected in transported rock, (2) At the surface, and subsurface (<=100 m), large deposits sandy to silted material from Elysium paleolake basin mixed with fine-grained sediments from Ma'adim Vallis are expected mostly in the upstream part of region B, (3) on the shoreline of the estuarine delta, abundant fine material from Elysium paleolake basin (evaporites, carbonates), mostly Amazonian in age are expected. The Ma'adini estuary is a favorable landing site for all the above mentioned science aspects, and .for its location. The site lies near the equator, which is favorable for the rover solar power supply, and at 1000m elevation, which is a favorable configuration for the descent system braking. Another advantage is the extent of the area of high scientific interest (33,000 sq km), which provides a good ellipse, and potential long study traverses.

Grin, E. A.↗

NASA NTRS1985

Carbon exchange between the mantle and the crust, and its effect upon the atmosphere - Today compared to archean time

Estimates of the midocean ridge mantle carbon flux, whose exchange of carbon with the earth's surface has over geological time influenced atmospheric CO2, can be made by estimating concentration ratios of carbon to helium in hydrothermal fluids and tholeiitic glasses, followed by their multiplication by the oceanic primordial He-3 flux. A net carbon flux from the mantle of 1 billion moles/yr would require less than 700 million years to generate the present day crustal carbon inventory. It is deduced that the atmosphere of 3 billion years ago contained at least two orders of magnitude more CO2 than it does today.

Des Marais, D. J.↗

NASA NTRS1982

Infrared airborne spectroradiometer survey results in the western Nevada area

The Mark II airborne spectroradiometer system was flown over several geologic test sites in western Nevada. The infrared mineral absorption bands were observed and recorded for the first time using an airborne system with high spectral resolution in the 2.0 to 2.5 micron region. The data show that the hydrothermal alteration zone minerals, carbonates, and other minerals are clearly visible in the airborne survey mode. The finer spectral features that distinguish the various minerals with infrared bands are also clearly visible in the airborne survey data. Using specialized computer pattern recognition methods, it is possible to identify mineralogy and map alteration zones and lithologies by airborne spectroradiometer survey techniques.

Collins, W.↗

NASA NTRS1985

A First Look at Airborne Imaging Spectrometer (AIS) Data in an Area of Altered Volcanic Rocks and Carbonate Formations, Hot Creek Range, South Central Nevada

Three flight lines of Airborne Imaging Spectrometer (AIS) data were collected in 128 bands between 1.2 and 2.4 microns in the Hot Creek Range, Nevada on July 25, 1984. The flight lines are underlain by hydrothermally altered and unaltered Paleozoic carbonates and Tertiary rhyolitic to latitic volcanics in the Tybo mining district. The original project objectives were to discriminate carbonate rocks from other rock types, to distinguish limestone from dolomite, and to discriminate carbonate units from each other using AIS imagery. Because of high cloud cover over the prime carbonate flight line and because of the acquisition of another flight line in altered and unaltered volcanics, the study has been extended to the discrimination of alteration products. In an area of altered and unaltered rhyolites and latites in Red Rock Canyon, altered and unaltered rock could be discriminated from each other using spectral features in the 1.16 to 2.34 micron range. The altered spectral signatures resembled montmorillonite and kaolinite. Field samples were gathered and the presence of montmorillonite was confirmed by X-ray analysis.

Feldman, S. C.↗

NASA NTRS2003

Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

Socki, Richard A.↗

NASA NTRS2019

Diamondites: Evidence for a Distinct Tectono-Thermal Diamond-Forming Event Beneath the Kaapvaal Craton

The petrogenesis and relationship of diamondite to well-studied monocrystalline and fibrous diamonds are poorly understood yet would potentially reveal new aspects of how diamond-forming fluids are transported through the lithosphere and equilibrate with surrounding silicates. Of twenty-two silicate- and oxide-bearing diamondites investigated, most yielded garnet intergrowths (n = 15) with major element geochemistry (i.e. Ca-Cr) classifying these samples as low-Ca websteritic or eclogitic. The garnet REE patterns fit an equilibrium model suggesting the diamond-forming fluid shares an affinity with high-density fluids (HDF) observed in fibrous diamonds, specifically on the join between the saline–carbonate end- members. The δ13C values for the diamonds range from -5.27 to -22.48 ‰ (V-PDB) with δ18O values for websteritic garnets ranging from +7.6 to +5.9 ‰ (V-SMOW). The combined C-O stable isotope data support a model for a hydrothermally altered and organic carbon-bearing subducted crustal source(s) for the diamond- and garnet-forming media. The nitrogen aggregation states of the diamonds require that diamondite-formation event(s) pre-dates fibrous diamond-formation and post-dates most of the gem monocrystalline diamond-formation events at Orapa. The modelled fluid compositions responsible for the precipitation of diamondites match the fluid-poor and fluid-rich (fibrous) monocrystalline diamonds, where all grow from HDFs within the saline-silicic-carbonatitic ternary system. However, while the nature of the parental fluid(s) share a common lithophile element geochemical affinity, the origin(s) of the saline, silicic, and/or carbonatitic components of these HDFs do not always share a common origin. Therefore, it is wholly conceivable that the diamondites are evidence of a distinct and temporally unconstrained tectono-thermal diamond-forming event beneath the Kaapvaal craton.

S Mikhail↗

NASA NTRS2013

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

NASA NTRS2013

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

NASA NTRS2001

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

Jahnke, L. L.↗

NASA NTRS2001

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

Extremely thermophilic microbial communities associated with the siliceous vent walls and outflow channel of Octopus Spring, Yellowstone National Park, have been examined for lipid biomarkers and carbon isotopic signatures. These data were compared with that obtained from representatives of three Aquificales genera. Thermocrinis ruber. "Thermocrinis sp. HI", Hydrogenobacter thermophilus TK-6, Aquifex pyrophilus and Aquifex aeolicus all contained phospholipids composed not only of the usual ester-linked fatty acids, but also ether-linked alkyls. The fatty acids of all cultured organisms were dominated by a very distinct pattern of n-C-20:1 and cy-C-21 compounds. The alkyl glycerol ethers were present primarily as CIS() monoethers with the expection of the Aquifex spp. in which dialkyl glycerol ethers with a boarder carbon-number distribution were also present. These Aquificales biomarker lipids were the major constituents in the lipid extracts of the Octopus Spring microbial samples. Two natural samples, a microbial biofilm growing in association with deposition of amorphous silica on the vent walls at 92 C, and the well-known 'pink-streamers community' (PSC), siliceous filaments of a microbial consortia growing in the upper outflow channel at 87 C were analyzed. Both the biofilm and PSC samples contained mono and dialkyl glycerol ethers with a prevalence of C-18 and C-20 alkyls. Phospholipid fatty acids were comprised of both the characteristic Aquificales n-C-20:1 and cy-C-21, and in addition, a series of iso-branched fatty acids from i-C-15:0 to i-C-21:0, With i-C-17:0 dominant in the PSC and i-C-19:0 in the biofilm, suggesting the presence of two major bacterial groups. Bacteriohopanepolyols were absent and the minute quantities of archaeol detected showed that Archaea were only minor constituents. Carbon isotopic compositions of the PSC yielded information about community structure and likely physiology. Biomass was C-13-depleted (10.9%) relative to available CO2 from the source water inorganic carbon pool with lipids further depleted by 6.3% relative to biomass The C-20-21 Aquificales fatty acids of the PSC were somewhat heavier than the iso-branched fatty acids. The carbon isotopic signatures of lipid biomarkers were also explored using a pure culture, T ruber, previously isolated from the PSC. Cells grown on C02 with O2 and both H2 and thiosulfate as electron donors were only slightly depleted (3.3%) relative to the C-source while cells grown on formate with O2 showed a major discrimination (19.7%), possibly the result of a metabolic branch point involving the assimilation of C-formate to biomass and the dissimilation to CO2 associated with energy production. T. ruber lipids were slightly heavier than biomass (+1.3%) whether cells were grown using CO2 or formate. Fatty acids from CO2 grown T. ruber cells were a so slightly heavier (average +2.1%) than biomass. The relatively depleted PSC C-20-21 fatty acids suggest that any associated Thermocrinis biomass would also be similarly depleted and much too light to be explained by growth on CO2. The C-fractionations determined with the pure culture suggest that growth of Thermocrinis in the PSC is more likely to occur on formate, presumably generated by geothermal activity. This study points to the value of the analysis of the structural and isotopic composition of lipid blomarkers both in pure culture studies, and in establishing community structure and physiology, as a complement to genomic profiles of microbial diversity. This is especially so when the members of the microbial community are novel and difficult to cultivate in the laboratory.

Jahnke, Linda L.↗

NASA NTRS2001

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

Jahnke, Linda L.↗

NASA NTRS2010

Discovery of Carbonate-Rich Outcrops in the Gusev Crater Columbia Hills by the MER Rover Spirit

The chemical composition, global abundance, distribution, and formation pathways of carbonates are central to understanding aqueous processes, climate, and habitability of early Mars. The Mars Exploration Rover (MER) Spirit analyzed a series of olivine-rich outcrops while descending from the summit region of Husband Hill into the Inner Basin of the Columbia Hills of Gusev Crater to the eastern edge of the El Dorado ripple field in late 2005. Reanalysis of Spirit s mineralogical data from the Moessbauer Spectrometer (MB) and the Miniature Thermal Emission Spectrometer (Mini-TES) and chemical data from the Alpha Particle X-Ray Spectrometer (APXS) in 2010, coupled with new laboratory data for carbonate-bearing samples, lead to identification of carbonate in one of the outcrops (Comanche) [Morris, R.V., et al., Science, 329, 421-424]. The carbonate is rich in magnesium and iron (Mc62Sd25Cc11Rh2, assuming all Ca and Mn is associated with the carbonate) and is a major component of the Comanche outcrops (16 to 34 wt.%). The mineralogical, chemical, and abundance data are constrained in multiple, mutually consistent ways by the MER analyses. For example, a low-Ca carbonate is required by the MB and APXS data and is consistent with Mini-TES data. Three spectral features attributable to fundamental infrared vibrational modes of low-Ca carbonate are present in the Mini-TES spectra of Comanche outcrops. The average composition of Comanche carbonate approximates the average composition of the carbonate globules in Martian meteorite ALH 84001. Analogy with ALH 84001, terrestrial, and synthetic carbonate globules suggests that Comanche carbonate precipitated from aqueous solutions under hydrothermal conditions at near neutral pH in association with volcanic activity during the Noachian era. Comanche outcrop morphology suggests they are remnants of a larger carbonate-bearing formation that evolved in ultramafic rock and then preferentially eroded by a combination of aeolian abrasion and chemical decomposition by exposure to acid-sulfate vapors/solutions. The high carbonate concentration in the Comanche outcrops supports climate models involving a CO2 greenhouse gas on a wet and warm early Mars and subsequent sequestering of at least part of that atmosphere in carbonate minerals.

Morris, Richard V.↗