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Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗

NASA NTRS1985

Planetary ecology; Proceedings of the Sixth International Symposium on Environmental Biogeochemistry, Santa Fe, NM, October 10-14, 1983

Topics presented include biological evolution and planetary chemistry; C-1 compounds; transport, deposition, and weathering; sulfur transformations; ground water; transformation processes for nitrogen oxides; and soils. Papers are presented on immunological studies on the organic matrix of recent and fossil invertebrate shells; biogenic gases in sediments deposited since Miocene times on the Walvis Ridge, South Atlantic Ocean; aspects of the biogeochemistry of Big Soda Lake, NV; mesophilic manganese-oxidizing bacteria from hydrothermal discharge areas at 21 deg North on the East Pacific Rise; and autotrophic growth and iron oxidation and inhibition kinetics of Leptospirillum ferrooxidans. Consideration is also given to thermophilic archaebacteria occurring in submarine hydrothermal areas; fate of sulfate in a soft-water, acidic lake; geochemical conditions in the ground water environment; microbial transformations as sources and sinks for nitrogen oxides; and the biogeochemistry of soil phosphorus.

Caldwell, D. E.↗

NASA NTRS1986

Aerosols in polluted versus nonpolluted air masses Long-range transport and effects on clouds

To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United States, aerosol and cloud-drop size distributions, elemental composition of aerosols as a function of size, and ionic content of cloud water were measured on Whiteface Mountain, NY, during the summers of 1981 and 1982. In several case studies, the data were cross-correlated with different air mass types - background continental, polluted continental, and maritime - that were advected to the sampling site. The results are the following: (1) Anthropogenic sources hundreds of kilometers upwind cause the small-particle (accumulation) mode number to increase from hundreds of thousands per cubic centimeter and the mass loading to increase from a few to several tens of micrograms per cubic meter, mostly in the form of sulfur aerosols. (2) A significant fraction of anthropogenic sulfur appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (3) Clouds in Atlantic maritime air masses have cloud drop spectra that are markedly different from those measured in continental clouds. The drop concentration is significantly lower, and the drop size spectra are heavily skewed toward large drops. (4) Effects of anthropogenic pollutants on cloud water ionic composition are an increase of nitrate by a factor of 50, an increase of sulfate by more than one order of magnitude, and an increase of ammonium ion by a factor of 7. The net effect of the changes in ionic concentrations is an increase in cloud water acidity. An anion deficit even in maritime clouds suggests an unknown, possibly biogenic, source that could be responsible for a pH below neutral, which is frequently observed in nonpolluted clouds.

Pueschel, R. F.↗

NASA NTRS1988

Collisions with ice-volatile objects: Geological implications

The collision of the Earth with extra-terrestrial ice-volatile bodies is proposed as a mechanism to produce rapid changes in the geologic record. These bodies would be analogs of the ice satellites found for the Jovian planets and suspected for comets and certain low density bodies in the Asteroid belt. Five generic end-members are postulated: (1) water ice; (2) dry ice: carbon-carbon dioxide rich, (3) oceanic (chloride) ice; (4) sulfur-rich ice; (5) ammonia hydrate-rich ice; and (6) clathrate: methane-rich ice. Due to the volatile nature of these bodies, evidence for their impact with the Earth would be subtle and probably best reflected geochemically or in the fossil record. Actual boloids impacting the Earth may have a variable composition, generally some admixture with water ice. However for discussion purposes, only the effects of a dominant component will be treated. The general geological effects of such collisions, as a function of the dominant component would be: (1) rapid sea level rise unrelated to deglaciation, (2) decreased oceanic pH and rapid climatic warming or deglaciation; (3) increased paleosalinities; (4) increased acid rain; (5) increased oceanic pH and rapid carbonate deposition; and (6) rapid climatic warming or deglaciation.

Wilde, P.↗

NASA NTRS2008

Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.

Smialek, James L.↗

NASA NTRS2008

Geochemical Properties of Rocks and Soils in Gusev Crater, Mars: APXS Results from Cumberland Ridge to Home Plate

The Mars Exploration Rover Spirit landed in Gusev crater on Jan. 4, 2004. Spirit has traversed the Gusev crater plains, ascended to the top of Husband Hill, and entered into the Inner Basin of the Columbia Hills. The Athena science payload onboard Spirit has recorded numerous measurements on the chemistry and mineralogy of materials encountered during nearly 2 Mars years of operation within the crater. Rocks and soils have been grouped into classes based upon their unique differences in mineralogy and chemistry [1-3]. Some of the most significant chemical discoveries include the composition of Adirondack class flood basalts [4-6]; high sulfur in Clovis and Peace Class rocks [7,2]; high P and Ti in Wishstone Class rocks [7,2]; composition of alkalic basalts [2,6]; very high S in Paso Robles class soils [7,2], and the possible occurrence of a smectite-like chemical composition in Independence class rocks [8]. Water has played a significant role in the alteration of rocks and soils in the Columbia Hills. The occurrence of goethite and ferric sulfate alone suggests that liquid water was involved in their formation [3]. The pervasively altered materials in Husband Hill outcrops and rocks may have formed by the aqueous alteration of basaltic rocks, volcaniclastic materials, and/or impact ejecta by solutions that were rich in acid-volatile elements [2]. The objective of this paper is to provide an update on the health of the Alpha Particle X-ray Spectrometer (APXS) and to expand the geochemical dataset from sol 470 to sol 1368. Specific objectives are to (1) update the rock and soil classifications, (2) characterize elemental relationships among the major rock and soil classes, and (3) evaluate the involvement of water in the formation or alteration of the materials in these classes.

Ming, D. W.↗

NASA NTRS1994

Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

Photosynthetic reaction centers from a variety of organisms have been isolated and characterized. The groups of prokaryotic photosynthetic organisms include the purple bacteria, the filamentous green bacteria, the green sulfur bacteria and the heliobacteria as anoxygenic representatives as well as the cyanobacteria and prochlorophytes as oxygenic representatives. This review focuses on structural and functional comparisons of the various groups of photosynthetic reaction centers and considers possible evolutionary scenarios to explain the diversity of existing photosynthetic organisms.

NASA Discipline Exobiology↗

NASA NTRS2005

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposits at Rio Tinto, Spain: Implications for Extant Life on Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth s largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗

NASA NTRS2005

Characterization of a Subsurface Biosphere in a Massive Sulfide Deposit At Rio Tinto, Spain: Implications For Extant Life On Mars

The recent discovery of abundant sulfate minerals, particularly Jarosite by the Opportunity Rover at Sinus Merdiani on Mars has been interpreted as evidence for an acidic lake or sea on ancient Mars [1,2], since the mineral Jarosite is soluble in liquid water at pH above 4. The most likely mechanism to produce sufficient protons to acidify a large body of liquid water is near surface oxidation of pyrite rich deposits [3]. The acidic waters of the Rio Tinto, and the associated deposits of Hematite, Goethite, and Jarosite have been recognized as an important chemical analog to the Sinus Merdiani site on Mars [4]. The Rio Tinto is a river in southern Spain that flows 100 km from its source in the Iberian pyrite belt, one of the Earth's largest Volcanically Hosted Massive Sulfide (VHMS) provinces, into the Atlantic ocean. The river originates in artesian springs emanating from ground water that is acidified by the interaction with subsurface pyrite ore deposits. The Mars Analog Rio Tinto Experiment (MARTE) has been investigating the hypothesis that a subsurface biosphere exists at Rio Tinto living within the VHMS deposit living on chemical energy derived from sulfur and iron minerals. Reduced iron and sulfur might provide electron donors for microbial metabolism while in situ oxidized iron or oxidants entrained in recharge water might provide electron acceptors.

Stoker, C. R.↗

NASA NTRS2018

Linking Improvements in Sulfur Dioxide Emissions to Decreasing Sulfate Wet Deposition by Combining Satellite and Surface Observations with Trajectory Analysis

Sulfur dioxide (SO2), a criteria pollutant, and sulfate (SO42) deposition are major environmental concerns in the eastern U.S. and both have been on the decline for two decades. In this study, we use satellite column SO2 data from the Ozone Monitoring Instrument (OMI), and SO42 wet deposition data from the NADP (National Atmospheric Deposition Program) to investigate the temporal and spatial relationship between trends in SO2 emissions and the downward sulfate wet deposition over the eastern U.S. from 2005 to 2015. To establish the relationship between SO2 emission sources and receptor sites, we conducted a Potential Source Contribution Function (PSCF) analysis using HYSPLIT back trajectories for five selected Air Quality System (AQS) sites - (Hackney, OH, Akron, OH, South Fayette, PA, Wilmington, DE, and Beltsville, MD) - in close proximity to NADP sites with large downward SO42 trends since 2005. Back trajectories were run for three summers (JJA) and three winters (DJF) and used to generate seasonal climatology PSCFs for each site. The OMI SO2 and interpolated NADP sulfate deposition trends were normalized and overlapped with the PSCF, to identify the areas that had the highest contribution to the observed drop. The results suggest that emission reductions along the Ohio River Valley have led to decreases in sulfate deposition in eastern OH and western PA (Hackney, Akron and South Fayette). Farther to the east, emission reductions in southeast PA resulted in improvements in sulfate deposition at Wilmington, DE, while for Beltsville, reductions in both the Ohio River Valley and nearby favorably impacted sulfate deposition. For Beltsville, sources closer than 300km from the site contribute roughly 56% observed deposition trends in winter, and 82% in summer, reflecting seasonal changes in transport pattern as well as faster oxidation and washout of sulfur in summer. This suggests that emissions and wet deposition are linked through not only the location of sources relative to the observing sites, but also to photochemistry and the weather patterns characteristic to the region, as evidenced by a west to east shift in the contribution between winter and summer. The method developed here is applicable to other regions with significant trends such as China and India, and can be used to estimate the potential benefits of emission reduction in those areas.

Acid depostion↗

NASA NTRS2004

Lunar and Planetary Science XXXV: Meteorites

The session "Meteorites" included the following reports:Description of a New Stony Meteorite Find from Bulloch County, Georgia; Meteorite Ablation Derived from Cosmic Ray Track Data Dhofar 732: A Mg-rich Orthopyroxenitic Achondrite Halogens, Carbon and Sulfur in the Tagish Lake Meteorite: Implications for Classification and Terrestrial Alteration; Electromagnetic Scrape of Meteorites and Probably Columbia Tiles; Pre-Atmospheric Sizes and Orbits of Several Chondrites; Research of Shock-Thermal History of the Enstatite Chondrites by Track, Thermoluminescence and Neutron-Activation (NAA) Methods; Radiation and Shock-thermal History of the Kaidun CR2 Chondrite Glass Inclusions; On the Problem of Search for Super-Heavy Element Traces in the Meteorites: Probability of Their Discovery by Three-Prong Tracks due to Nuclear Spontaneous Fission Trace Element Abundances in Separated Phases of Pesyanoe, Enstatite Achondrite; Evaluation of Cooling Rate Calculated by Diffusional Modification of Chemical Zoning: Different Initial Profiles for Diffusion Calculation; Mineralogical Features and REE Distribution in Ortho- and Clinopyroxenes of the HaH 317 Enstatite Chondrite Dhofar 311, 730 and 731: New Lunar Meteorites from Oman; The Deuterium Content of Individual Murchison Amino Acids; Clues to the Formation of PV1, an Enigmatic Carbon-rich Chondritic Clast from the Plainview H-Chondrite Regolith Breccia ;Numerical Simulations of the Production of Extinct Radionuclides and ProtoCAIs by Magnetic Flaring.

Source record↗

NASA NTRS2004

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗

NASA NTRS1992

Origin and early evolution of photosynthesis

Photosynthesis was well-established on the earth at least 3.5 thousand million years ago, and it is widely believed that these ancient organisms had similar metabolic capabilities to modern cyanobacteria. This requires that development of two photosystems and the oxygen evolution capability occurred very early in the earth's history, and that a presumed phase of evolution involving non-oxygen evolving photosynthetic organisms took place even earlier. The evolutionary relationships of the reaction center complexes found in all the classes of currently existing organisms have been analyzed using sequence analysis and biophysical measurements. The results indicate that all reaction centers fall into two basic groups, those with pheophytin and a pair of quinones as early acceptors, and those with iron sulfur clusters as early acceptors. No simple linear branching evolutionary scheme can account for the distribution patterns of reaction centers in existing photosynthetic organisms, and lateral transfer of genetic information is considered as a likely possibility. Possible scenarios for the development of primitive reaction centers into the heterodimeric protein structures found in existing reaction centers and for the development of organisms with two linked photosystems are presented.

NASA Program Exobiology↗

NASA NTRS1992

Upper-atmosphere Aerosols: Properties and Natural Cycles

The middle atmosphere is rich in its variety of particulate matter, which ranges from meteorite debris, to sulfate aerosols, to polar stratospheric ice clouds. Volcanic eruptions strongly perturb the stratospheric sulfate (Junge) layer. High-altitude 'noctilucent' ice clouds condense at the summer mesopause. The properties of these particles, including their composition, sizes, and geographical distribution, are discussed, and their global effects, including chemical, radiative, and climatic roles, are reviewed. Polar stratospheric clouds (PSCs) are composed of water and nitric acid in the form of micron-sized ice crystals. These particles catalyze reactions of chlorine compounds that 'activate' otherwise inert chlorine reservoirs, leading to severe ozone depletions in the southern polar stratosphere during austral spring. PSCs also modify the composition of the polar stratosphere through complex physiocochemical processes, including dehydration and denitrification, and the conversion of reactive nitrogen oxides into nitric acid. If water vapor and nitric acid concentrations are enhanced by high-altitude aircraft activity, the frequency, geographical range, and duration of PSCs might increase accordingly, thus enhancing the destruction of the ozone layer (which would be naturally limited in geographical extent by the same factors that confine the ozone hole to high latitudes in winter). The stratospheric sulfate aerosol layer reflects solar radiation and increases the planetary albedo, thereby cooling the surface and possibly altering the climate. Major volcanic eruptions, which increase the sulfate aerosol burden by a factor of 100 or more, may cause significant global climate anomalies. Sulfate aerosols might also be capable of activating stratospheric chlorine reservoirs on a global scale (unlike PCSs, which represent a localized polar winter phenomenon), although existing evidence suggests relatively minor perturbations in chlorine chemistry. Nevertheless, if atmospheric concentrations of chlorine (associated with anthropogenic use of chlorofluorocarbons) continue to increase by a factor of two or more in future decades, aircraft emissions of sulfur dioxide and water vapor may take on greater significance.

Turco, Richard P.↗

NASA NTRS2009

Laser Ablation Increases PEM/Catalyst Interfacial Area

An investigational method of improving the performance of a fuel cell that contains a polymer-electrolyte membrane (PEM) is based on the concept of roughening the surface of the PEM, prior to deposition of a thin layer of catalyst, in order to increase the PEM/catalyst interfacial area and thereby increase the degree of utilization of the catalyst. The roughening is done by means of laser ablation under carefully controlled conditions. Next, the roughened membrane surface is coated with the thin layer of catalyst (which is typically platinum), then sandwiched between two electrode/catalyst structures to form a membrane/ele c t - rode assembly. The feasibility of the roughening technique was demonstrated in experiments in which proton-conducting membranes made of a perfluorosulfonic acid-based hydrophilic, protonconducting polymer were ablated by use of femtosecond laser pulses. It was found that when proper combinations of the pulse intensity, pulse-repetition rate, and number of repetitions was chosen, the initially flat, smooth membrane surfaces became roughened to such an extent as to be converted to networks of nodules interconnected by filaments (see Figure 1). In further experiments, electrochemical impedance spectroscopy (EIS) was performed on a pristine (smooth) membrane and on two laser-roughened membranes after the membranes were coated with platinum on both sides. Some preliminary EIS data were interpreted as showing that notwithstanding the potential for laser-induced damage, the bulk conductivities of the membranes were not diminished in the roughening process. Other preliminary EIS data (see Figure 2) were interpreted as signifying that the surface areas of the laser-roughened membranes were significantly greater than those of the smooth membrane. Moreover, elemental analyses showed that the sulfur-containing molecular groups necessary for proton conduction remained intact, even near the laser-roughened surfaces. These preliminary results can be taken as indications that laser-roughened PEMs should function well in fuel cells and, in particular, should exhibit current and power densities greater than those attainable by use of smooth membranes.

Whitacre, Jay↗

NASA NTRS2003

Radiation Synthesis of New Molecules on Jupiter's Icy Satellites

Spectra of Jupiter's icy satellites reveal surfaces dominated by water-ice, minor amounts of SO2 and CO2, and (for Europa) H2O2 along with hydrated materials. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons significantly modify the chemical composition of these moons' surfaces in times ranging from a few years for Europa to thousands of years for Callisto at micrometer depths. Appropriate laboratory studies examining relevant volatile and non-volatile materials under low-temperature radiation conditions can provide information on likely radiation chemical mechanisms, on the stability and evolution of species, and on new species awaiting detection. Although the molecules detected on the icy moons are relatively simple, predicting their responses to radiation in space remains difficult. One problem is that there is a dearth of fundamental data examining solid-phase reactions. Our laboratory experiments have focused on infrared studies (2.5 to 25 microns) of a few simple irradiated ices. We have measured the spectra of proton-irradiated H2O ice containing SO2, H2S, and/or CO2. Ices with H2O/SO2 or H2O/H2S ratios of 3 and 30 have been irradiated at 86 K, 110 K, and 132 K. In irradiated H2O + SO2 ices new ions have been identified: SO4(-2), HSO4(-) and H3O(+). After warming to 260 K the residual spectrum is similar to that of H2SO4. Ices with H2O + H2S form SO2. After warming to 175 K, the residual sample matches the spectrum of hydrated H2SO4. H2O + CO2 ice forms carbonic acid, H2CO3 which is stable to temperatures near 230 K. In addition, OCS has been detected in irradiated ices containing H2O + SO2 + CO2. The radiation half-life of SO2 and H2S in H2O has been calculated. Our results give compelling evidence for the presence of new species awaiting detection. Future experiments will examine the signatures of these ices and hydrated materials in the 1 to 5 micron region, where possible weaker overtone bands may occur. In addition, absolute strengths for both the fundamental and overtone bands will be determined. Finally, good arguments can be made, based on current information, for remote sensing observations that have spectral coverage to at least 5 microns on the long wavelength end. This range would include some of the characteristic bands of H2O, H2O2, CO2, SO2, H2CO3, H2S, and OCS.

Moore, M. H.↗

NASA NTRSDate not supplied

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

NASA NTRS1986

Archaebacterial phylogeny: perspectives on the urkingdoms

Comparisons of complete 16S ribosomal RNA sequences have been used to confirm, refine and extend earlier concepts of archaebacterial phylogeny. The archaebacteria fall naturally into two major branches or divisions, I--the sulfur-dependent thermophilic archaebacteria, and II--the methanogenic archaebacteria and their relatives. Division I comprises a relatively closely related and phenotypically homogeneous collection of thermophilic sulfur-dependent species--encompassing the genera Sulfolobus, Thermoproteus, Pyrodictium and Desulfurococcus. The organisms of Division II, however, form a less compact grouping phylogenetically, and are also more diverse in phenotype. All three of the (major) methanogen groups are found in Division II, as are the extreme halophiles and two types of thermoacidophiles, Thermoplasma acidophilum and Thermococcus celer. This last species branches sufficiently deeply in the Division II line that it might be considered to represent a separate, third Division. However, both the extreme halophiles and Tp. acidophilum branch within the cluster of methanogens. The extreme halophiles are specifically related to the Methanomicrobiales, to the exclusion of both the Methanococcales and the Methanobacteriales. Tp. acidophilum is peripherally related to the halophile-Methanomicrobiales group. By 16S rRNA sequence measure the archaebacteria constitute a phylogenetically coherent grouping (clade), which excludes both the eubacteria and the eukaryotes--a conclusion that is supported by other sequence evidence as well. Alternative proposals for archaebacterial phylogeny, not based upon sequence evidence, are discussed and evaluated. In particular, proposals to rename (reclassify) various subgroups of the archaebacteria as new kingdoms are found wanting, for both their lack of proper experimental support and the taxonomic confusion they introduce.

NASA Discipline Exobiology↗