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At least 559 records · Page 31

Understanding Microbial Contributions to Planetary Atmosphere

Should our search of distant, extrasolar planetary atmospheres encounter evidence of life, that evidence will most likely be the gaseous products of microorganisms. Our biosphere was exclusively microbial for over 80 percent of its history and, even today, microbes strongly influence atmospheric composition. Life's greatest environmental impact arises from its capacity for harvesting energy and creating organic matter. Microorganisms catalyze the equilibration of C, S and transition metal species at temperatures where such reactions can be very slow in the absence of life. Sunlight has been harvested through photosynthesis to create enormous energy reservoirs that exist in the form of coexisting reservoirs of reduced, organic C and S stored in Earth's crust, and highly oxidized species (oxygen, sulfate and ferric iron) stored in the crust, oceans and atmosphere. Our civilization taps that storehouse of energy by burning fossil fuels. As astrobiologists, we identify the chemical consequences of distant biospheres as expressed in the atmospheres of their planets. Our approach must recognize that planets, biospheres and atmospheres evolve and change. For example, a tectonically more active early Earth hosted a thermophilic, non-photosynthetic biosphere and a mildly reducing, carbon dioxide-rich and oxygen-poor atmosphere. Microorganisms acquired energy by consuming hydrogen and sulfide and producing a broad array of reduced C and S gases, most notably, methane. Later, diverse types of bacterial photosynthesis developed that enhanced productivity but were incapable of splitting water to produce oxygen. Later, but still prior to 2.6 billion years ago, oxygenic photosynthesis developed. We can expect to encounter distant biospheres that represent various stages of evolution and that coexist with atmospheres ranging from mildly reducing to oxidizing compositions. Accordinaly, we must be prepared to interpret a broad range of atmospheric compositions, all containing signatures of life. Remarkably little is known about the composition of our own earlier atmosphere, particularly prior to the rise of oxygen levels some 2.0 to 2.2 billion years ago. Thus, field and laboratory observations and theoretical simulations should be conducted to examine the relationships between the structure and function of microbial ecosystems and their gaseous products. Ecosystems that are analogs of our ancient biosphere (e.g., based upon chemosynthesis or non-oxygenic photosynthesis, thermophilic and subsurface communities, etc.) should be included. Because key environmental parameters such as temperature and levels of hydrogen, carbon dioxide and oxygen varied during planetary evolution, their consequences for microbial ecosystems should be explored.

DesMarais, David J.↗

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Jacobson, N. S.↗

Flammability of Heterogeneously Combusting Metals

Most engineering materials, including some metals, most notably aluminum, burn in homogeneous combustion. 'Homogeneous' refers to both the fuel and the oxidizer being in the same phase, which is usually gaseous. The fuel and oxidizer are well mixed in the combustion reaction zone, and heat is released according to some relation like q(sub c) = delta H(sub c)c[((rho/rho(sub 0))]exp a)(exp -E(sub c)/RT), Eq. (1) where the pressure exponent a is usually close to unity. As long as there is enough heat released, combustion is sustained. It is useful to conceive of a threshold pressure beyond which there is sufficient heat to keep the temperature high enough to sustain combustion, and beneath which the heat is so low that temperature drains away and the combustion is extinguished. Some materials burn in heterogeneous combustion, in which the fuel and oxidizer are in different phases. These include iron and nickel based alloys, which burn in the liquid phase with gaseous oxygen. Heterogeneous combustion takes place on the surface of the material (fuel). Products of combustion may appear as a solid slag (oxide) which progressively covers the fuel. Propagation of the combustion melts and exposes fresh fuel. Heterogeneous combustion heat release also follows the general form of Eq.(1), except that the pressure exponent a tends to be much less than 1. Therefore, the increase in heat release with increasing pressure is not as dramatic as it is in homogeneous combustion. Although the concept of a threshold pressure still holds in heterogeneous combustion, the threshold is more difficult to identify experimentally, and pressure itself becomes less important relative to the heat transfer paths extant in any specific application. However, the constants C, a, and E(sub c) may still be identified by suitable data reduction from heterogeneous combustion experiments, and may be applied in a heat transfer model to judge the flammability of a material in any particular actual-use situation. In order to support the above assertions, two investigations are undertaken: 1) PCT data are examined in detail to discover the pressure dependence of heterogeneous combustion experiment results; and 2) heterogeneous combustion in a PCT situation is described by a heat transfer model, which is solved first in simplified form for a simple actual-use situation, and then extended to apply to PCT data reduction (combustion constant identification).

Jones, Peter D.↗

An impact-induced terrestrial atmosphere and iron-water reactions during accretion of the Earth

Shock wave data and theoretical calculations were used to derive models of an impact-generated terrestrial atmosphere during accretion of the Earth. The models showed that impacts of infalling planetesimals not only provided the entire budget of terrestrial water but also led to a continuous depletion of near-surface layers of water-bearing minerals of their structural water. This resulted in a final atmospheric water reservoir comparable to the present day total water budget of the Earth. The interaction of metallic iron with free water at the surface of the accreting Earth is considered. We carried out model calcualtions simulating these processes during accretion. It is assumed that these processes are the prime source of the terrestrial FeO component of silicates and oxides. It is demonstrated that the iron-water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed. In order to obtain the necessary amount of terrestrial water, slightly heterogeneous accretion with initially 36 wt% iron planetesimals, as compared with a homogeneous value of 34 wt% is required.

Lange, M. A.↗

Moessbauer spectroscopic studies of iron-doped rutile.

Moessbauer spectra were obtained of single crystal and powdered samples of rutile (TiO2) doped to about one percent by weight in isotopically enriched iron. It is shown that the oxidation state may be reversibly altered in situ. After reduction, the oxygen neighbors of the dopant ion are apparently shifted to accomodate the larger ferrous ion. The agreement of calculated quadrupole splittings with experimental results suggests that impurities and oxygen vacancies are uniformly distributed in powdered samples, giving the dopant ions an 'ideal lattice' local environment. The differences between the single crystal and powder sample hyperfine parameters are attributed to variations in stoichiometry, charge compensation mechanisms, or other diffusion related parameters.

Stampfl, P. P.↗

Friction and wear of polyethylene oxide polymer having a range of molecular weights

Sliding friction and wear experiments were conducted at light loads (25 to 250 g) with various molecular weights of the polyethylene oxide polymer sliding on itself and iron. Results of the experimental investigation indicate that: (1) the coefficient of friction for the polymer decreases with increasing molecular weight; (2) friction coefficient is higher for the polymer sliding on itself than it is for the polymer sliding on iron; (3) at sufficiently high loads localized surface melting occurs and the friction coefficient is the same for the polymer sliding on itself and iron; (4) fracture cracks develop in the sliding wear track at higher but not lower sliding velocities, reflecting a strain rate sensitivity to crack initiation, and (5) the friction coefficient for the polymer sliding on iron increases with the formation of a polymer film on the iron surface.

Buckley, D. H.↗

Simulation of the Viking biology experiments - An overview

In the present paper, ground-based investigations of the Viking Martian biology data, which have resulted in reasonable simulations of these data, are reviewed. These simulations, which in strong oxidants, UV-treated materials, iron-containing clays, or iron salts were used as Martian analogs, are capable of explaining the ambiguity between the GCMS (gas-chromatography mass-spectrometry) experiments, in which no organic compounds were found on Mars, and the Labeled Release experiments, in which added organics were decomposed.

Klein, H. P.↗

The composition of the Martian dark regions: Observations and analysis

Near infrared telescopic spectrophotometry for dark regions is present and interpreted using laboratory studies of iron bearing mineral mixtures and terrestrial oxidized and unoxidized basalts. Upon closer inspection (by spacecraft) the telescopic dark regions were found to consist of large scale intermixtures of bright soil (aeolian dust) and dark materials. The dark materials themselves consist of an intimate physical association of very fine grained ferric oxide bearing material with relatively high near infrared reflectance and darker, relatively unoxidized rocks or rock fragments. While these two components could exist finely intermixed in a soil, a number of lines of evidence indicate that the usual occurrence is probably a thin coating of physically bound oxidized material. The coated rocks are dark and generally clinopyroxene bearing. The shallow band depths and low overall reflectances indicate that opaque minerals such as magnetite are probably abundant.

Singer, R. B.↗

Ion bombardment and adsorption studies on ilmenite (FeTiO3) by X-ray photoelectron spectroscopy

The effects of 5 KeV argon and oxygen ion bombardment on FeTiO3 (ilmenite) at low temperatures have been studied using X-ray photoelectron spectroscopy (XPS). Also, using this same technique, the adsorption of O2, NO, N2O, and CO at 300 K and the adsorption of O2 and D2O at 150K have been studied. Argon and oxygen ion bombardment of ilmenite have confirmed earlier studies on metal oxides that argon ions generally reduce the anion species while oxygen ions generally oxidize the anion species. The two iron states involved were Fe sup +2 and Fe sup O. The reduction of Ti sup +4 was not verified although a significant shift in the Ti(2p1,3) binding energies toward the metallic state was observed after oxygen ion bombardment at low temperatures. At temperatures above 150K, O2 adsorbs dissociatively on ilmenite while D2O adsorbs molecularly below 170K. Above 300 K No, N2O, and CO do not appear to adsorb dissociatively. Low temperature adsorption of D2O was found to be inhibited by predosing the ilmenite with O2.

Schulze, P. D.↗

The LiAl/FeS2 battery power source for the future

Advanced high power density rechargeable batteries are currently under development. These batteries have the potential of greatly increasing the power and energy densities available for space applications. Depending on whether the system is optimized for high power or high energy, values up to 150 Wh/kg and 2100 W/kg (including hardware) are projected. This is due to the fact that the system uses a high conductivity molten salt electrolyte. The electrolyte also serves as a separator layer with unlimited freeze thaw capabilities. Life of 1000 cycles and ten calendar years is projected. The electrochemistry consists of a lithium aluminum alloy negative electrode, iron disulfide positive electrode, and magnesium oxide powder immobilized molten salt electrolyte. Processed powders are cold compacted into circular discs which are assembled into bipolar cell hardware with peripheral ceramic salts. The culmination of the work will be a high energy battery of 40 kWh and a high power battery of 28 kWh.

Briscoe, J. Douglass↗

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗

Magnetotactic bacteria on Earth and on Mars

Continued interest in the possibility of evidence for life in the ALH84001 Martian meteorite has focused on the magnetite crystals. This review is structured around three related questions: is the magnetite in ALH84001 of biological or non-biological origin, or a mixture of both? does magnetite on Earth provide insight to the plausibility of biogenic magnetite on Mars? could magnetotaxis have developed on Mars? There are credible arguments for both the biological and non-biological origin of the magnetite in ALH84001, and we suggest that more studies of ALH84001, extensive laboratory simulations of non-biological magnetite formation, as well as further studies of magnetotactic bacteria on Earth will be required to further address this question. Magnetite grains produced by bacteria could provide one of the few inorganic traces of past bacterial life on Mars that could be recovered from surface soils and sediments. If there was biogenic magnetite on Mars in sufficient abundance to leave fossil remains in the volcanic rocks of ALH84001, then it is likely that better-preserved magnetite will be found in sedimentary deposits on Mars. Deposits in ancient lakebeds could contain well-preserved chains of magnetite clearly indicating a biogenic origin.

Review, Tutorial↗

Nutrition in Space: Benefits on Earth

History has often proven the criticality for adequate nutrition to ensure expedition success. Space exploration will be no different, with the exception of the certainty that food will not be found along the journey. Ensuring the health and safety of astronauts is critical and nutrition will serve several functions to that end. Nutritional assessment of International Space Station (ISS) crewmembers not only serves to evaluate the nutritional health of individuals, but also allows a better understanding of how space flight affects nutritional requirements, and how nutrition can serve in mitigating the negative effects of weightlessness on the human. Available data suggest that the nutritional status of astronauts is compromised during and after flight. Inadequate dietary intake and subsequent weight loss are often considered hallmarks of space flight, although exceptions to this do exist, and provide hope. However, beyond energy intake, specific nutrient issues also exist. Several vitamins, including D and folate, are affected in space travelers. Hematological and antioxidant defense systems are impacted, with increased iron storage, and increased markers of oxidative damage. Bone loss during space flight remains a critical challenge. Ground-based studies have proven that nutrition is a potent modulator of the bone response to simulated weightlessness. Protein and sodium are two nutrients which tend to exacerbate bone resorption and loss, likely mediated through acid base balance. Defining nutrient requirements, and being able to provide and maintain those nutrients on exploration missions, will be critical for maintaining crew member health. Both flight and ground-based research provide a unique situation, one where healthy individuals are put in a unique and challenging environment. A full understanding of the role of nutrition during space flight will not only enhance crew health and safety during flight, but will also expand our understanding of the role of nutrition in health of those remaining on Earth.

Smith, Scott M.↗

Meteoritic Material Recovered from the 07 March 2018 Meteorite Fall into the Olympic Coast National Marine Sanctuary

On 07 March 2018 at 20:05 local time (08 March 03:05 UTC), a dramatic meteor occurred over Olympic Coast National Marine Sanctuary (OCNMS) off of the Washington state coast (“OCNMS fall”, henceforth). Data to include seismometry (from both on-shore and submarine seismometers), weather radar imagery (Figure 1), and a moored weather buoy, were used to accurately identify the fall site. The site was visited by the exploration vessel E/V Nautilus (Ocean Exploration Trust) on 01 July 2018 [1] and by the research vessel R/V Falkor (Schmidt Ocean Institute) from 03-06 June 2019. Remotely operated vehicles (ROVs) from both vessels were used to search for meteorites and sample seafloor sediments. These expeditions performed the first attempts to recover meteorites from a specific observed fall in the open ocean. Analysis of weather radar data indicates that this fall was unusually massive and featured meteorites of unusually high mechanical toughness, such that large meteorites were disproportionately produced compared to other meteorite falls (Figure 2)[2-4]. We report the recovery of many (>100) micrometeorite-sized melt spherules and other fragments, and one small (~1mm3 ) unmelted meteorite fragment identified to date. Approximately 80% of the fragments were recovered from a single sample, collected from a round pit in the seafloor sediment. Melt spherules are almost exclusively type I iron-rich spherules with little discernible oxidation. Analyses are currently underway to attempt to answer the primary science question by identifying the parent meteorite type. Also, differences in the number and nature of samples collected by Nautilus and Falkor reveal a distinct loss rate to oxidation over the 15 months following the fall that is useful to inform future recovery efforts.

Fries, M.↗

Design Through Simulation of a Molecular Sieve Column for Treatment of MON-3

The presence of water in propellant-grade MON-3 is a concern in the Aerospace Industry. NASA Johnson Space Center (JSC), White Sands Test Facility (WSTF) Propulsion Department has evaluated many types of molecular sieves for control of iron, the corrosion product of water in Mixed Oxides of Nitrogen (MON-3). In 1995, WSTF initiated laboratory and pilot-scale testing of molecular sieve type 3A for removal of water and iron. These tests showed sufficient promise that a series of continuous recycle tests were conducted at WSTF. Periodic samples of the circulating MON-3 solution were analyzed for water (wt %) and iron (ppm, wt). This test column was modeled as a series of transfer units; i. e., each unit represented the height equivalent of a theoretical plate. Such a model assumes there is equilibrium between the adsorbent material and the effluent stream from the unit. Operational and design parameters were derived based on the simulation results. These parameters were used to predict the design characteristics of a proposed molecular sieve column for removal of water and iron from MON-3 at the NASA Kennedy Space Center (KSC). In addition, these parameters were used to simulate a small, single-pass operation column at KSC currently used for treating MON-3. The results of this work indicated that molecular sieve type 3A in 1/16 in. diameter pellets, in a column 2.5 ft. in diameter, 18 ft. in height, and operated at 25 gpm is adequate for the required removal of water and iron from MON-3.

Swartz, A. Ben↗

Moessbauer search for ferric oxide phases in lunar materials and simulated lunar materials

Moessbauer studies were carried out on lunar fines and on simulated lunar glasses containing magnetic-like precipitates with the primary objective of determining how much, if any, ferric oxide is present in the lunar soils. Although unambiguous evidence of lunar Fe(3+) phases was not obtained, an upper limit was estimated from different portions of the Moessbauer spectra to be between 0.1 and 0.4 wt.% (as Fe3O4). A smaller than 62 microns fraction of 15021,118 showed 0.5 wt.% ferromagnetic iron at 300 K in as-returned condition. After heating to 650 C in an evacuated, sealed quartz tube for 1400 hours, the same sample exhibited 1 wt.% ferromagnetic iron at room temperature. An accompanying decrease in excess absorption area near zero velocity was noted. Thus, the result of the vacuum heat treatment was to convert fine grained iron to larger particles, apparently without the oxidation effects commonly reported.

Forester, D. W.↗

Investigation of a possible solar-wind darkening of the lunar surface by photoelectron spectroscopy.

Detailed sequential study by photoelectron spectroscopy of the change in valence states of iron in Fe2O3, Fe3O4, FeO, and Fe foil samples, showing that chemical reduction does take place on the sample surface when argon ion bombardment occurs. These spectra give evidence that, after prolonged ion bombardment, the surface of all four samples consisted predominantly of iron in the metallic state. Argon ion sputtering of 15 silicate and oxide samples under similar experimental conditions produced surface darkening only in samples containing iron. Monitoring of the photoelectron peak of carbon during the experiment indicates that ion-bombardment darkening is not due to the buildup of hydrocarbon surface contaminants in the oil-free high-vacuum system used by the authors. On the basis of these studies, it is concluded that solar-wind bombardment should be included as one of the possible mechanisms for producing darkening of the lunar surface.

Yin, L. I.↗

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

Kasting, James F.↗