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NASA NTRS2017

Large Sulphur Isotope Fractionations in Martian Sediments at Gale Crater

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in S-34. Measured values of δS-34 range from -47 +/- 14% to 28 +/- 7%, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Curiosity↗
NASA NTRS2002

Lipid Biomarkers for Methanogens in Hypersaline Cyanobacterial Mats for Guerrero Negro, Baja California Sur

Analyses of sediments from the vicinity of active methane seeps have uncovered a particular suite of lipid biomarker patterns that characterize methane consuming archaea and their syntrophic, sulfate reducing partners. These isoprenoid biomarkers, largely identified by their anomalously light carbon isotopic signatures, have been a topic of intense research activity and are recorded in numerous methane-rich environments from Holocene to Cenozoic. This phenomenon has implications for depleted kerogens at 2.7 Ga on early Earth (Hinrichs 2002). In contrast, the lipid biosignatures of methane producing archaea are not readily identified through distinct isotopic labels and have received comparably little attention in analyses of archaea in environmental samples. Indeed, environmental analyses generally detect only free archaeal lipids, not the intact, polar molecules found in the membrane of living organisms. As part of the Ames NAI, the 'Early Microbial Ecosystem Research Group' (EMERG) is working to understand microbial processes in the hypersaline cyanobacterial mats growing in the salt evaporation ponds of the Exportadora de Sal at Guerrero Negro, Baja California Sur, Mexico. The aim of this study was to develop methods by which we could identify the organisms responsible for methane generation in this environment. While the ester-bound fatty acids, hopanoids and wax esters provide a means to identify most of the bacterial components of these mats, the archaea which Ere evidently present through genomic assays and the fact of intense methane production (Hoehler et al. 200l), have not been identified through their corresponding lipid signatures. Archaeal core lipids present a number of analytical challenges. The core lipids of methanogens comprise C20, C40 and sometimes C25 isoprenoid chains, linked through ether bonds to glycerol. As well as archaeal (C20), sn-2- and sn-3-hydroxyarchaeol are associated particularly with methylotrophic methanogens. Recently, we have also identified a dihydroxyarchaeol in a hyperthermophilic methanogen (Summons et al. 2002). Additional structural diversity is encoded into the polar head groups that are attached to the glycerol ether cores. The C20 core lipids are readily analyzed by GC-MS as their volatile trimethylsilyl derivatives while compounds with intact polar head groups can only be detected using LC-MS approaches. Our approach was to utilize the alternative of an ether cleavage reagent (BBr3 vs. HI) and a hydride reducing agent to convert all ether lipids to hydrocarbon in order to provide a vertical profile of quantitative information that might be matched to methane fluxes. We have found that while conventional acid hydrolysis and HI treatment will destroy hydroxyarchaeols, molecular information remains intact through use of BBr3 for ether cleavage. This method revealed the presence of traces of biphytane and various ether alkyls associated with some sulfate reducing bacteria within the mat structure. An interesting, and potentially valuable, byproduct of the method utilizing HI was the identification of abundant homohopanoids after superhydride reduction. Evidently present as sulfur-bound diagenetic products these hopanoids are likely cyanobacterial biomarkers in the early stages of diagenetic preservation.

Jahnke, Linda L.↗
NASA NTRS1984

Early solar system aqueous activity - Sr isotope evidence from the Orgueil CI meteorite

The Sr isotopic composition and Rb-87/Sr-86 ratio have been measured in carbonates and sulfate separated from the Orgueil meteorite in order to determine the time when liquid water may have acted on the parent body. Both of the studied phases probably precipitated from aqueous solution. The results show that carbonate deposition occurred contemporaneously with parent body formation or shortly after it, probably within 100 Myr. On the other hand, at least some of the calcium sulfate seems to have been formed recently.

Macdougall, J. D.↗
NASA NTRS1992

Aqueous geochemistry on Mars: Possible clues from salts and clays in SNC meteorites

All subgroups of the shergottite, nakhlite, and chassignite (SNC) meteorites contain traces of water precipitated minerals that include various combinations of carbonates, sulfates, halides, ferric oxides, and aluminosilicate clays of preterrestrial origin. Oxygen three-isotope analysis of thermally extracted bulk water has confirmed that at least some of the water in SNC's is, indeed, extraterrestrial. A mixture of aqueous precipitates found in the SNC's, comprising smectite, illite, and gypsum (with minor halite +/- calcite and hematite), provides a self-consistent, though not unique, model for the bulk elemental composition of surface sediments at the Viking Lander sites. Therefore, if the salts and clays in SNC's are truly linked to aqueous alteration and soil formation on Mars, then the suite of SNC secondary minerals might provide the best currently available insight into near-surface martian chemistry.

Gooding, James L.↗
NASA NTRS2011

Measuring Sulfur Isotope Ratios from Solid Samples with the Sample Analysis at Mars Instrument and the Effects of Dead Time Corrections

The Sample Analysis at Mars (SAM) instrument suite comprises the largest science payload on the Mars Science Laboratory (MSL) "Curiosity" rover. SAM will perform chemical and isotopic analysis of volatile compounds from atmospheric and solid samples to address questions pertaining to habitability and geochemical processes on Mars. Sulfur is a key element of interest in this regard, as sulfur compounds have been detected on the Martian surface by both in situ and remote sensing techniques. Their chemical and isotopic composition can belp constrain environmental conditions and mechanisms at the time of formation. A previous study examined the capability of the SAM quadrupole mass spectrometer (QMS) to determine sulfur isotope ratios of SO2 gas from a statistical perspective. Here we discuss the development of a method for determining sulfur isotope ratios with the QMS by sampling SO2 generated from heating of solid sulfate samples in SAM's pyrolysis oven. This analysis, which was performed with the SAM breadboard system, also required development of a novel treatment of the QMS dead time to accommodate the characteristics of an aging detector.

Franz, H. B.↗
NASA NTRS2013

Shock Experiments on Basalt - Ferric Sulfate Mixes at 21 GPa & 49 GPa and their Relevance to Martian Meteorite Impact Glasses

Large abundance of Martian atmospheric gases and neutron-induced isotopic excesses as well as Rb-Sr isotopic variations determined in some impact glasses in basaltic shergottites (e.g., Shergotty #DBS, Zagami #H1 and EET79001 #27, #8 and #104) provide definitive evidence for the occurrence of a Martian regolith component in their constituent mineral assemblages. Some of these glass-es, known as gas-rich impact-melts (GRIM), contain numerous micron-sized iron sulfide blebs along with minor amounts of iron sulfate particulates. As these GRIM glasses contain a Martian regolith component and as iron sulfates (but not sulfides) are found to occur abundantly on the Mars surface, we suggested that the sulfide blebs in GRIMs were likely generated by shock-reduction of the parental iron sulfate bearing regolith material that had been incorporated into the cavities/crevices of basaltic host rock prior to the impact event on Mars. To test whether the sulfates could be reduced to sulfides by impact shock, we carried out laboratory shock experiments on a basalt plus ferric sulfate mixture at 49 GPa at the Caltech Shock Wave Laboratory and at 21 GPa at Johnson Space Center (JSC) Experimental Impact Laboratory. The experimental details and the preliminary results for the Caltech 49 GPa experiment were presented at LPSC last year. Here, we report the results for the 21 GPa experiment at JSC and compare these results to obtain further insight into the mechanism of the bleb formation in the GRIM glasses.

Rao, M. N.↗
NASA NTRS2004

Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

Source record↗
NASA NTRS1992

Attempts to comprehend Martian surface processes through interpretation of the oxygen isotopic compositions of carbonates in SNC meteorites

The SNC meteorites are known to contain trace quantities of a variety of secondary minerals such as carbonates, sulfates, and aluminosilicates. Since these constituents are thought to be mostly preterrestrial in origin, their study has the potential to provide rigorous constraints on the nature of martian weathering processes. However, this line of investigation is potentially complicated by the presence within the meteorite samples of any additional weathering products produced by terrestrial processes. Examination of such terrestrial components is important since weathering processes that affect meteorite samples following their fall to Earth might have some bearing on the nature of analogous processes at the surface of Mars. It is obviously necessary to try and distinguish which secondary components in SNC meteorites are terrestrial in origin from those that are preterrestrial. Herein consideration is made of the stable isotopic compositions of weathering products in two SNC meteorites: EET A79001 (a sample collected from Antarctica) and Nakhla (a fall from Egypt, 1911).

Wright, I. P.↗
NASA NTRSDate not supplied

Bulk Oxygen Isotopic Compositions of Anhydrous Interplanetary Dust Particles: Indication of an 16O-Poor Reservoir In The Outer Solar System

The oxygen isotopic ratios of ancient solar system materials reflect the isotopically distinct reservoirs in which they formed or were altered. These compositions are generally explained by mixing of material derived from an 16O-rich reservoir and material from an 16O-poor reservoir thought to be isotopically heavy H2O. Evidence of this 16O-poor reservoir is scarce and includes cosmic symplectite (COS), probable silicates in an interplanetary dust particle (IDP), and sulfates in a cometary xenolith. These materials have 17O and 18O enrichments between ~150–200 ‰, which agree with predictions for self-shielding and photodissociation of CO. The ‘cometary’ 16O-poor materials indicate alteration or formation in the outer solar system. The bulk O isotopic compositions of IDPs thought to have cometary origins may also harbor evidence of this primordial 16O-poor reservoir. Here we report the bulk O compositions of anhydrous IDPs and discuss the nebular reservoirs from which they derived

A N Nguyen↗
NASA NTRS2012

Laboratory Shock Experiments on Basalt - Iron Sulfate Mixes at Approximately 40-50 GPa and Their Relevance to the Martian Regolith Component Present in Shergottites

Basaltic shergottites such as Shergotty, Zagami and EET79001 contain impact melt glass pockets that are rich in Martian atmospheric gases [1] and are known as gas-rich impact-melt (GRIM) glasses. These glasses show evidence for the presence of a Martian regolith component based on Sm and Kr isotopic studies [2]. The GRIM glasses are sometimes embedded with clusters of innumerable micron-sized iron-sulfide blebs associated with minor amounts of iron sulfate particles [3, 4]. These sulfide blebs are secondary in origin and are not related to the primary igneous sulfides occurring in Martian meteorites. The material comprising these glasses arises from the highly oxidizing Martian surface and sulfur is unlikely to occur as sulfide in the Martian regoilith. Instead, sulfur is shown to occur as sulfate based on APXS and Mossbauer results obtained by the Opportunity and Spirit rovers at Meridiani and Gusev [5]. We have earlier suggested that the micron-sized iron sulfide globules in GRIM glasses were likely produced by shock-reduction of iron sulfate occurring in the regolith at the time when the GRIM glasses were produced by the meteoroid impact that launched the Martian meteorites into space [6]. As a result of high energy deposition by shock (approx. 40-60 GPa), the iron sulfate bearing phases are likely to melt along with other regolith components and will get reduced to immiscible sulfide fluid under reducing conditions. On quenching, this generates a dispersion of micron-scale sulfide blebs. The reducing agents in our case are likely to be H2 and CO which were shock-implanted from the Martian atmosphere into these glasses along with the noble gases. We conducted lab simulation experiments in the Lindhurst Laboratory of Experimental Geophysics at Caltech and the Experimental Impact Laboratory at JSC to test whether iron sulfide globules can be produced by impact-driven reduction of iron sulfate by subjecting Columbia River Basalt (CRB) and ferric sulfate mixtures to shock pressures between 40 and 50 GPa under reducing conditions. The experimental products from the recovered samples were analyzed by SEM and microprobe techniques at JSC.

Rao, M. N.↗
NASA NTRS1980

The origin and evolution of sulfur in an Archean volcano-sedimentary basin, Deer Lake area, Minnesota

Rocks of the Deer Lake area, northcentral Minnesota, consist of Archean (age greater than 2.6 billion years) metasediments and metavolcanics intruded by mafic layered sills. Geologic and sulfur isotopic data suggest that sulfides in the sediments are bacteriogenic, having formed in response to the activity of sulfate reducing bacteria during diagenesis. Deposition of the sediments appears to have occurred in a deep marine basin with restricted circulation of sea water. The bulk of the sulfur in the igneous rocks is of deep seated origin, but basal contacts of the sills show evidence of assimilation of biogenic sulfur from the intruded sediments. This assimilation of biogenic sulfur is the primary geochemical control of local Cu-Ni sulfide mineralization.

Nicol, D. L.↗
NASA NTRS2008

Proceedings of the 39th Lunar and Planetary Science Conference

Sessions with oral presentations include: A SPECIAL SESSION: MESSENGER at Mercury, Mars: Pingos, Polygons, and Other Puzzles, Solar Wind and Genesis: Measurements and Interpretation, Asteroids, Comets, and Small Bodies, Mars: Ice On the Ground and In the Ground, SPECIAL SESSION: Results from Kaguya (SELENE) Mission to the Moon, Outer Planet Satellites: Not Titan, Not Enceladus, SPECIAL SESSION: Lunar Science: Past, Present, and Future, Mars: North Pole, South Pole - Structure and Evolution, Refractory Inclusions, Impact Events: Modeling, Experiments, and Observations, Mars Sedimentary Processes from Victoria Crater to the Columbia Hills, Formation and Alteration of Carbonaceous Chondrites, New Achondrite GRA 06128/GRA 06129 - Origins Unknown, The Science Behind Lunar Missions, Mars Volcanics and Tectonics, From Dust to Planets (Planetary Formation and Planetesimals):When, Where, and Kaboom! Astrobiology: Biosignatures, Impacts, Habitability, Excavating a Comet, Mars Interior Dynamics to Exterior Impacts, Achondrites, Lunar Remote Sensing, Mars Aeolian Processes and Gully Formation Mechanisms, Solar Nebula Shake and Bake: Mixing and Isotopes, Lunar Geophysics, Meteorites from Mars: Shergottite and Nakhlite Invasion, Mars Fluvial Geomorphology, Chondrules and Chondrule Formation, Lunar Samples: Chronology, Geochemistry, and Petrology, Enceladus, Venus: Resurfacing and Topography (with Pancakes!), Overview of the Lunar Reconnaissance Orbiter Mission, Mars Sulfates, Phyllosilicates, and Their Aqueous Sources, Ordinary and Enstatite Chondrites, Impact Calibration and Effects, Comparative Planetology, Analogs: Environments and Materials, Mars: The Orbital View of Sediments and Aqueous Mineralogy, Planetary Differentiation, Titan, Presolar Grains: Still More Isotopes Out of This World, Poster sessions include: Education and Public Outreach Programs, Early Solar System and Planet Formation, Solar Wind and Genesis, Asteroids, Comets, and Small Bodies, Carbonaceous Chondrites, Chondrules and Chondrule Formation, Chondrites, Refractory Inclusions, Organics in Chondrites, Meteorites: Techniques, Experiments, and Physical Properties, MESSENGER and Mercury, Lunar Science Present: Kaguya (SELENE) Results, Lunar Remote Sensing: Basins and Mapping of Geology and Geochemistry, Lunar Science: Dust and Ice, Lunar Science: Missions and Planning, Mars: Layered, Icy, and Polygonal, Mars Stratigraphy and Sedimentology, Mars (Peri)Glacial, Mars Polar (and Vast), Mars, You are Here: Landing Sites and Imagery, Mars Volcanics and Magmas, Mars Atmosphere, Impact Events: Modeling, Experiments, and Observation, Ice is Nice: Mostly Outer Planet Satellites, Galilean Satellites, The Big Giant Planets, Astrobiology, In Situ Instrumentation, Rocket Scientist's Toolbox: Mission Science and Operations, Spacecraft Missions, Presolar Grains, Micrometeorites, Condensation-Evaporation: Stardust Ties, Comet Dust, Comparative Planetology, Planetary Differentiation, Lunar Meteorites, Nonchondritic Meteorites, Martian Meteorites, Apollo Samples and Lunar Interior, Lunar Geophysics, Lunar Science: Geophysics, Surface Science, and Extralunar Components, Mars, Remotely, Mars Orbital Data - Methods and Interpretation, Mars Tectonics and Dynamics, Mars Craters: Tiny to Humongous, Mars Sedimentary Mineralogy, Martian Gullies and Slope Streaks, Mars Fluvial Geomorphology, Mars Aeolian Processes, Mars Data and Mission,s Venus Mapping, Modeling, and Data Analysis, Titan, Icy Dwarf Satellites, Rocket Scientist's Toolbox: In Situ Analysis, Remote Sensing Approaches, Advances, and Applications, Analogs: Sulfates - Earth and Lab to Mars, Analogs: Remote Sensing and Spectroscopy, Analogs: Methods and Instruments, Analogs: Weird Places!. Print Only Early Solar System, Solar Wind, IDPs, Presolar/Solar Grains, Stardust, Comets, Asteroids, and Phobos, Venus, Mercury, Moon, Meteorites, Mars, Astrobiology, Impacts, Outer Planets, Satellites, and Rings, Support for Mission Operations, Analog Education and Public Outreach.

Source record↗
NASA NTRS1992

The carbon isotope biogeochemistry of acetate from a methanogenic marine sediment

The delta C-13 value of porewater acetate isolated from the anoxic sediments of Cape Lookout Bight (North Carolina) ranged from -17.6 percent in the sulfate reduction zone to -2.8 percent in the underlying methanogenic zone. The large C-13 enrichment in the sulfate-depleted sediments appears to be associated with the dissimilation of acetate to CH4 and CO2. Fractionation factors for that process were estimated to be 1.032 +/- 0.014 and 1.036 +/- 0.019 for the methyl and carboxyl groups. A subsurface maximum in delta C-13 of the total acetate molecule, as well as the methyl and carboxyl carbons at 10-15 cm depth within the sediment column, indicate that changes in the relative rates of acetate cycling pathways occur in the methanogenic zone. The methyl group of the acetate was depleted in C-13 by 7-14 percent relative to the carboxyl moiety. The intramolecular heterogeneity may be the result of both synthetic and catabolic isotope effects.

Blair, N. E.↗
NASA NTRS2003

MN Carbonates in the Martian Meteorite Nakhla: Possible Evidence of Brine Evaporation

The importance of secondary phases in martian meteorites lies in their potential to provide clues about the martian environments responsible for their formation. During this study, we analyzed a number of carbonate-bearing fracture surfaces from the Nakhla meteorite. Here we describe the physical and chemical properties of several manganese-calcium-rich siderites. Additionally, we describe a potential model for the formation and alteration of these carbonates, and we suggest constraints on the conditions responsible for their precipitation. Nakhla is an olivine-bearing clinopyroxenite with minor amounts of feldspar, FeS, and Fe oxides. Secondary mineral assemblages include vein filling clay with embedded iron oxides, a calcium sulfate, amorphous silica, chlorapatite, halite and carbonates. Bridges and Grady suggested that the carbonates in Nakhla formed from brine evaporation. Isotope studies of the Mn rich siderite are also consistent with formation from hydrothermal fluids with an upper T constraint of ~170 C.

Bailey, J. V.↗
NASA NTRS1993

3.4-Billion-year-old biogenic pyrites from Barberton, South Africa: sulfur isotope evidence

Laser ablation mass spectroscopy analyses of sulfur isotopic compositions of microscopic-sized grains of pyrite that formed about 3.4 billion years ago in the Barberton Greenstone Belt, South Africa, show that the pyrite formed by bacterial reduction of seawater sulfate. These data imply that by about 3.4 billion years ago sulfate-reducing bacteria had become active, the oceans were rich in sulfate, and the atmosphere contained appreciable amounts (>>10(-13) of the present atmospheric level) of free oxygen.

NASA Discipline Exobiology↗
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 NTRS2015

Gusev-Meridiani-Type Soil Component Dissolved in Some Shock Glasses in Shergottites

Modal analysis, based on APXS, MiniTES and Mossbauer results obtained at Gusev and Meridiani sites on Mars, indicates that Martian soils consist predominantly of igneous minerals such as olivine, pyroxene and feldspar (approximately70 - 80%), with the balance consisting of alteration minerals such as sulfates, silica and chlorides]. These studies also showed that soil alteration did not occur in-situ and igneous and alteration components are derived from different sources. Below, we analyse the chemical abundance data obtained from shock glasses in shergottites using mass balance mixing models. In these models, the two main end members used are (a) host rock chemical composition and (b) the GM soils average composition as the second component. Here, we consider the S-bearing phases as indicators of added alteration phases in the shock glasses and GM soils. Although the S-bearing phase in shock glasses occurs as micron sized sulfide blebs, we showed in earlier abstracts that sulfur was originally present as sulfate in impact glass-precursor materials and was subsequently reduced to sulfide during shock melting. This conclusion is based on results obtained from S-K XANES studies, Fe/S atomic ratios in sulfide blebs and 34S/32S isotopic measurements in these sulfide blebs. Additionally, sulfur in several EET79001 Lith. A glasses is found to correlate positively with Al2O3 and CaO (and negatively with FeO and MgO), suggesting the presence of Al- and Ca- sul-fate-bearing phases. The distribution of the 87Sr/86Sr iso-topic ratios determined in Lith. A glasses (,27 &,188 and,54) indicate that Martian soil gypsum and host rock material were mixed with each other in the glass precursors. In some vugs in Lith A glass,27 detected gypsum laths. Furthermore, the Martian regolith-de-rived component (where sulfur typically occurs as sul-fate) is identified in these glasses by determining neutron produced isotopic excesses/deficits in 80Kr and 149Sm isotopes. Moreover, the suggestion that the large amount of sulfur found in,507 was sourced from pyrrhotite in the host rock, would require that excessive quantities of host rock would need to be stripped of sulfur to make this sulfide-rich glass. These results provide ample evidence that S occurred as sulfate and was added to glass precursor materials prior to impact shock.

Ross, D. K.↗