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PubMed1990

Microbial metabolism of tholin.

In this paper, we show that a wide variety of common soil bacteria are able to obtain their carbon and energy needs from tholin (a class of complex organic heteropolymers thought to be widely distributed through the solar system; in this case tholin was produced by passage of electrical discharge through a mixture of methane, ammonia, and water vapor). We have isolated aerobic, anaerobic, and facultatively anaerobic bacteria which are able to use tholin as a sole carbon source. Organisms which metabolize tholin represent a variety of bacterial genera including Clostridium, Pseudomonas, Bacillus, Acinetobacter, Paracoccus, Alcaligenes, Micrococcus, Corynebacterium, Aerobacter, Arthrobacter, Flavobacterium, and Actinomyces. Aerobic tholin-using bacteria were first isolated from soils containing unusual or sparse carbon sources. Some of these organisms were found to be facultatively anaerobic. Strictly anaerobic tholin-using bacteria were isolated from both carbon-rich and carbon-poor anaerobic lake muds. In addition, both aerobic and anaerobic tholin-using bacteria were isolated from common soil collected outside the laboratory building. Some, but not all, of the strains that were able to obtain carbon from tholin were also able to obtain their nitrogen requirements from tholin. Bacteria isolated from common soils were tested for their ability to obtain carbon from the water-soluble fraction, the ethanol-soluble fraction, and the water/ethanol-insoluble fraction of the tholin. Of the 3.5 x 10(7) bacteria isolated per gram of common soils, 1.7, 0.5, and 0.2%, respectively, were able to obtain their carbon requirements from the water-soluble fraction, the ethanol-soluble fraction and the water/ethanol-insoluble fraction of the tholin. The palatability of tholins to modern microbes may have implications for the early evolution of microbial life on Earth. Tholins may have formed the base of the food chain for an early heterotrophic biosphere before the evolution of autotrophy on the early Earth. Where tholins are present on other planets, they could possibly be metabolized by contaminant microorganisms transported to these bodies via spacecraft. Thus, the presence of tholins should be taken into account when evaluating the planetary quarantine requirements for probes to other planets.

Amino Acids↗

PubMed1990

Could organic matter have been preserved on Mars for 3.5 billion years?

3.5 billion years (byr) ago, when it is thought that Mars and Earth had similar climates, biological evolution on Earth had made considerable progress, such that life was abundant. It is therefore surmised that prior to this time period the advent of chemical evolution and subsequent origin of life occurred on Earth and may have occurred on Mars. Analysis for organic compounds in the soil buried beneath the Martian surface may yield useful information regarding the occurrence of chemical evolution and possibly biological evolution. Calculations based on the stability of amino acids lead to the conclusion that remnants of these compounds, if they existed on Mars 3.5 byr ago, might have been preserved buried beneath the surface oxidizing layer. For example, if phenylalanine, an amino acid of average stability, existed on Mars 3.5 byr ago, then 1.6% would remain buried today, or 25 pg-2.5 ng of C g-1 Martian soil may exist from remnants of meteoritic and cometary bombardment, assuming that 1% of the organics survived impact.

Amino Acids↗

PubMed1990

Deuterium enrichment in the primitive ices of the protosolar nebula.

We have estimated the D/H ratio that may have been present in the primitive ices in the protosolar nebula. Using observations of the CH3D/CH4 ratio in the outer planets, we developed two simple but limiting models which constrain the amount of dilution that deuterated volatiles which were contributed to the planetary atmospheres by evaporated primordial ices may have undergone by mixing with the original hydrogen envelopes. The models suggest that the D/H ratio in these ices was probably somewhere between a few times 10(-4) and 10(-3). These planetary-atmosphere-derived results are compared with other solar system bodies thought to contain primitive material and with D/H ratios observed in interstellar polyatomic molecules.

Atmosphere↗

PubMed1991

Plasma discharge in N2 + CH4 at low pressures: experimental results and applications to Titan.

We report the yields of gaseous hydrocarbons and nitriles produced in a continuous flow, low-dose, cold plasma discharge excited in a 10% CH4, 90% N2 atmosphere at 295 K and pressures p of 17 and 0.24 mbar, and use the results to compute expected abundances of minor constituents in Titan's atmosphere. These experiments are, by design, relevant to the atmospheric chemistry induced by cosmic rays in Titan's troposphere and (at the lower pressure) to chemistry initiated by Saturnian magnetospheric electrons and other charged particle sources which excite stratospheric aurorae. At p = 17 mbar, 59 gaseous species including 27 nitriles are detected in overall yield 4.0 (C + N) atoms incorporated into products per 100 eV (heV). At p = 0.24 mbar, 19 species are detected, including six nitriles and three other unidentified N-bearing compounds; the yield is 0.79 (C + N)/heV, a mild decrease with pressure. The types of molecules formed change more markedly, with high degrees of multiple bonding at 0.24 mbar prevailing over more H-saturated molecules at 17 mbar. The molecules and yields at 0.24 mbar bear a striking resemblance to the minor constituents found in Titan's atmosphere, all of which are abundant products in the laboratory experiment. Using the altitude-integrated flux of charged particle energy deposition at Titan, the laboratory yields at p = 0.24 mb, and a simple eddy mixing model, we compute absolute stratospheric column abundances and mole fractions. These are found to be in very good agreement with the Voyager IRIS observations. Except for the primarily photochemical products, C2H6 and C3H8, the match is much better than that obtained by photochemical-kinetic models, demonstrating that properly designed laboratory experiments are directly applicable to modeling radiation-chemical processes in planetary atmospheres. On the basis of this agreement we expect CH3-C triple bond N (ethanenitrile = acetonitrile) CH2=CH-CH=CH2 (1,3-butadiene), CH2=C=CH2 (1,2-propadiene = allene), and CH2=CH-C triple bond CH (1-buten-3-yne) to be present at mol fractions X > 10(-9), and CH2=CH-C triple bond N (propenenitrile), CH3-CH=CH2 (propene), and CH3-CH2-C triple bond N (propanenitrile) at X > 10(-10) in Titan's atmosphere.

Astronomical Phenomena↗

PubMed1991

CO2 condensation and the climate of early Mars.

A one-dimensional, radiative-convective climate model was used to reexamine the question of whether early Mars could have been kept warm by the greenhouse effect of a dense, CO2 atmosphere. The new model differs from previous models by considering the influence of CO2 clouds on the convective lapse rate and on the the planetary radiation budget. Condensation of CO2 decreases the lapse rate and, hence, reduces the magnitude of the greenhouse effect. This phenomenon becomes increasingly important at low solar luminosities and may preclude warm (0 degree C), globally averaged surface temperatures prior to approximately 2 billion years ago unless other greenhouse gases were present in addition to CO2 and H2O. Alternative mechanisms for warming early Mars and explaining channel formation are discussed.

Atmosphere↗

PubMed1991

Derivation of midinfrared (5-25 micrometers) optical constants of some silicates and palagonite.

The midinfrared 2000-400 cm-1 (5-25 micrometers) optical constants (real (n) and imaginary (k) indices of refraction) are presented for: (1) pyrophyllite; (2) kaolinite; (3) serpentine; (4) montmorillonite; (5) saponite; (6) palagonite; and (7) orthopyroxene. Comparison of the values derived here with those previously presented for serpentine, montmorillonite, and palagonite is generally quite good and discrepancies between values are probably due to either chemical differences between the actual samples or different techniques used to derive the values. For montmorillonite, saponite, and palagonite we were able to derive optical constants in the region of the H2O-bending fundamental near 6 micrometers. We find that if a pellet of pure material can be produced with a mirror-like surface then the optical constants of clays and other noncohesive materials can be readily derived.

Aluminum Silicates↗

PubMed1991

Troposphere-stratosphere interactions in a one-dimensional model of Jovian photochemistry.

A simple one-dimensional model of the Jovian atmosphere including the coupling between a rapidly mixed troposphere and a stagnant stratosphere is presented. We treat analytically the case of a chemically unreactive species flowing downward through the stratosphere and troposphere with a constant flux. The calculated concentration profile has a maximum value approximately one atmospheric scale height above the tropopause. The corresponding mixing ratio rapidly decreases in the lower stratosphere. The contrast between the peak stratosphere and tropopause concentrations reflects the variation between the lower stratosphere and upper troposphere eddy diffusion coefficients. Numerical simulations of unreactive CO and C2H6, considering high-altitude photochemical sources (yielding downward fluxes to the troposphere) and deep troposphere thermochemical sources, demonstrate that upper troposphere abundances may have a large photochemical contribution. Recent observations of CO near 5 bar can be reproduced by a model using any one of three different tropospheric eddy diffusion profiles: a constant value of approximately 10(8) cm2 sec-1, a constant value of < or approximately 10(4) cm2 sec-1, or a two-layer model with a rapidly mixed (10(8) cm2 sec-1) layer below 20 bar and a slower mixing layer (10(4) cm2 sec-1) between 100 mbar and 20 bar. In the latter two scenarios, the photochemical source is an important and/or dominant source of upper tropospheric CO. However, the upper tropospheric C2H6 abundances are distinctly different among the three cases. These calculations suggest objectives for higher spectral resolution observations, critical vertical scales for planning experiments on future missions to Jupiter, and predictions that can be tested with the Galileo probe mass spectrometer.

Atmosphere↗

PubMed1991

Gas release from comets.

Water ice was shown experimentally to retain trapped gases beyond the transformation temperature of amorphous ice to cubic ice. The amount of retained gases, which emerge during the transformation of cubic ice to hexagonal ice and when the ice evaporates, depends linearly on the thickness of the ice layer. Implications to comets are discussed.

Carbon Dioxide↗

PubMed1991

Titan's surface and troposphere, investigated with ground-based, near-infrared observations.

New observations of Titan's near-infrared spectrum (4000-5000 cm-1) combined with points taken from Fink and Larson's (1979) spectrum (4000-12500 cm-1) provide information on Titan's haze, possible clouds, surface albedo, and atmospheric abundance of H2. In the near-infrared, the main features in Titan's spectrum result from absorption of solar radiation by CH4. The strength of this absorption varies considerably with wavelength, allowing us to probe various atmospheric levels down to the surface itself by choosing specific wavelengths for analysis. At 4715 cm-1, the pressure-induced S(1) fundamental band of H2 lies in the wings of CH4 bands. Based on current values for the CH4 line parameters, Titan's spectrum can be best interpreted with a volume mixing ratio of H2 between 0.5 and 1.0%. Our observations suggest the existence of an optically thin CH4 cloud layer. The optical depths that we derive for Titan's haze and clouds are small enough to allow us to sense the surface of Titan at 4900, 6250, and 7700 cm-1. The most plausible interpretation of the albedos determined at these wavenumbers suggests a surface dominated by "dirty" water ice. A global ethane ocean is not compatible with these albedos.

Atmosphere↗

PubMed1991

CH4/NH3/H2O spark tholin: chemical analysis and interaction with Jovian aqueous clouds.

The organic solid (tholin) produced by spark discharge in a CH4 + NH3 + H2O atmosphere is investigated, along with the separable components of its water-soluble fraction. The chemistry of this material serves as a provisional model for the interaction of Jovian organic heteropolymers with the deep aqueous clouds of Jupiter. Intact (unhydrolyzed) tholin is resolved into four chemically distinct fractions by high-pressure liquid chromatography (HPLC). Gel filtration chromatography reveals abundant components at molecular weights approximately or equal to 600-700 and 200-300 Da. Gas chromatography/mass spectrometry of derivatized hydrolysis products of unfractionated tholin shows about 10% by mass protein and nonprotein amino acids, chiefly glycine, alanine, aspartic acid, beta-alanine, and beta-aminobutyric acid, and 12% by mass other organic acids and hydroxy acids. The stereospecificity of alanine is investigated and shown to be racemic. The four principal HPLC fractions yield distinctly different proportions of amino acids. Chemical tests show that small peptides or organic molecules containing multiple amino acid precursors are a possibility in the intact tholins, but substantial quantities of large peptides are not indicated. Candidate 700-Da molecules have a central unsaturated, hydrocarbon- and nitrile-rich core, linked by acid-labile (ester or amide) bonds to amino acid and carboxylic acid side groups. The core is probably not HCN "polymer." The concentration of amino acids from tholin hydrolysis in the lower aqueous clouds of Jupiter, about 0.1 micromole, is enough to maintain small populations of terrestrial microorganisms even if the amino acids must serve as the sole carbon source.

Amino Acids↗

PubMed1992

Survival of microorganisms in smectite clays: implications for Martian exobiology.

Manned exploration of Mars may result in the contamination of that planet with terrestrial microbes, a situation requiring assessment of the survival potential of possible contaminating organisms. In this study, the survival of Bacillius subtilis, Azotobacter chroococcum, and the enteric bacteriophage MS2 was examined in clays representing terrestrial (Wyoming type montmorillonite) or Martian (Fe(3+)-montmorillonite) soils exposed to terrestrial and Martian environmental conditions of temperature and atmospheric pressure and composition, but not to UV flux or oxidizing conditions. Survival of bacteria was determined by standard plate counts and biochemical and physiological measurements over 112 days. Extractable lipid phosphate was used to measure microbial biomass, and the rate of 14C-acetate incorporation into microbial lipids was used to determine physiological activity. MS2 survival was assayed by plaque counts. Both bacterial types survived terrestrial or Martian conditions in Wyoming montmorillonite better than Martian conditions in Fe(3+)-montmorillonite. Decreased survival may have been caused by the lower pH of the Fe(3+)-montmorillonite compared to Wyoming montmorillonite. MS2 survived simulated Mars conditions better than the terrestrial environment, likely due to stabilization of the virus caused by the cold and dry conditions of the simulated Martian environment. The survival of MS2 in the simulated Martian environment is the first published indication that viruses may be able to survive in Martian type soils. This work may have implications for planetary protection for future Mars missions.

Azotobacter↗

PubMed1992

The relative abundance of ethane to acetylene in the Jovian stratosphere.

The observed ratio of C2H6 to C2H2 in the Jovian stratosphere increases from approximately 55 at 2 mbar to approximately 277 at 12 mbar. In current photochemical models this ratio typically increases between 2 and 12 mbar by a factor of < or = 3. Recent laboratory kinetics studies on the reaction between C2H3 and H2 to form C2H4 suggest an efficient chemical mechanism for hydrogenation of C2H2 to C2H6. Inclusion of this scheme as part of a comprehensive updated model for hydrocarbon photochemistry in the atmosphere of Jupiter provides an explanation of the altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in the key rate constants at low temperatures is illustrated, identifying needs for additional laboratory measurements. Since the key reaction rate constants decrease with decreasing temperature, the hydrogenation of C2H2 as proposed predicts a qualitatively decreasing trend in the C2H6/C2H2 value with decreasing distance from the Sun. The observed variation between Jupiter and Saturn is consistent with this prediction.

Acetylene↗

PubMed1992

Hydrocarbon nucleation and aerosol formation in Neptune's atmosphere.

Photodissociation of methane at high altitude levels in Neptune's atmosphere leads to the production of complex hydrocarbon species such as acetylene (C2H2), ethane (C2H6), methylacetylene (CH3C2H), propane (C3H8), diacetylene (C4H2), and butane (C4H8). These gases diffuse to the lower stratosphere where temperatures are low enough to initiate condensation. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either homogeneous, heterogeneous, or ion-induced nucleation. Homogeneous nucleation will not be important for any of the hydrocarbon species considered; however, both heterogeneous and ion-induced nucleation should be possible on Neptune for most of the above species. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the particular species, the abundance of the condensable species, the temperature at which the vapor becomes supersaturated, and the number and type of condensation nuclei or ions available. Typical saturation ratios required for observable particle formation rates on Neptune range from approximately 3 for heterogeneous nucleation of methane in the upper troposphere to greater than 1000 for heterogeneous nucleation of methylacetylene, diacetylene, and butane in the lower stratosphere. Thus, methane clouds may form slightly above, and stratospheric hazes far below, their saturation levels. When used in conjunction with the results of detailed models of atmospheric photochemistry, our nucleation models place realistic constraints on the altitude levels at which we expect hydrocarbon hazes or clouds to form on Neptune.

Atmosphere↗

PubMed1992

The photolysis of NH3 in the presence of substituted acetylenes: a possible source of oligomers and HCN on Jupiter.

Photolysis of NH3 in the presence of propyne yields dimethylketazine (4) as the main product along with dimethylketimine, isopropylamine, and propioazine (7). Dimethylketazine and isopropylamine are the principal reaction products when the photolysis is performed at 198 K. The conversion to dimethylketazine is about 35 times greater at 198 K because it is not volatile and condenses on the wall of the photolysis cell out of the UV flux. Photolysis of dimethylketazine at 185 nm yields acetonitrile and small amounts of N-methyldimethylketimine (8). Photolysis of 8 gives acetonitrile. Photolysis of NH3 in the presence of 2-butyne gives the cis and trans isomers of 2-butene as the principal products along with the corresponding azine (9). Photolysis of azine 9 yields acetonitrile and propionitrile. Photolysis of hydrazine in the presence of propyne yields acetonitrile and isopropylamine but no azines were detected as reaction products. Quantum yields and percentage conversion to products are reported. These studies show that acetylenic hydrocarbons formed by the photolysis of methane in the stratosphere of Jupiter may react with radicals formed by NH3 photolysis to give nonvolatile yellow-brown polymers, dialkylazines, alkylnitriles, and eventually HCN. This scenario accounts for the observation of both HCN and chromophores on Jupiter.

Acetonitriles↗

PubMed1989

A corner-reflector mixer mount for far infrared wavelengths.

A new type of corner-reflector mixer mount, which has the advantages of ease of fabrication and assembly as well as frequency versatility, has been designed and constructed. The mixer works with arbitrary antenna lengths > or = 4 lambda with the reflector to antenna spacing adjusted to give a strong and symmetric central lobe. The predicted response patterns have been experimentally verified for various antenna lengths and operating frequencies between 800 and 2000 GHz. An important design feature is the incorporation of a microstrip matching network which eliminates IF impedance mismatch and provides mechanical isolation of the whisker antenna.

Astronomy↗

PubMed1992

Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms.

Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies.

Alkanes↗

PubMed1988

Rate of production, dissolution and accumulation of biogenic solids in the ocean.

The equatorial current system, by its response to global circulation changes, provides a unique recording mechanism for long range climatic oscillations. A permanent record of the changes in rate of upwelling and organic production is generated in the equatorial deep sea sediments, particularly by such biogenic components which are unaffected by secondary dissolution. In order to determine the rates of accumulation of various sedimentary components, a reliable differential measurement of age of the strata must be obtained. Various approaches to this problem are reviewed, and sources of error discussed. Secondary dissolution of calcium carbonate introduces a substantial and variable difference between the dissolution-modified, and hence a priori unknown, rate of deposition on one hand and the rate of accumulation, derivable from the observed concentration, on the other. The cause and magnitude of these variations are of importance, particularly since some current dating schemes are based on assumed constancy in the rate of accumulation of this and, in some cases, also all other sedimentary components. The concepts used in rate evaluation are discussed with emphasis on the difference between the state of dissolution, an observable property of the sediment, and the rate of dissolution, a parameter that requires deduction of the carbonate fraction dissolved, and of the time differential. As a most likely cause of the enhanced state of dissolution of the interglacial carbonate sediments is proposed the lowered rates of biogenic production and deposition, which cause longer exposure of the carbonate microfossils to corrosion in the bioturbated surface layer of the sediment. Historical perspective is included in the discussion in view of the dedication of the Symposium to Hans Pettersson, the leader of the Swedish Deep Sea Expedition 1947-1948, an undertaking that opened a new era in deep sea research and planetary dynamics.

Animals↗

PubMed1991

Results of TV imaging of Phobos (Experiment VSK-Fregat).

From February to March 1989 the Phobos 2 spacecraft took 37 TV images of Phobos at a distance of 190-1100 km. These images complement Mariner-9 and Viking data by providing higher-resolution coverage of a large region West of the crater Stickney (40-160 degrees W) and by providing disk-resolved measurements of surface brightness at a greater range of wavelengths and additional phase angles. These images have supported updated mapping and characterization of large craters and grooves, and have provided additional observations of craters' and grooves' bright rims. Variations in surface visible/near-infrared color ratio of almost a factor of 2 have been recognized; these variations appear to be associated with the ejecta of specific large impact craters. Updated determinations of satellite mass and volume allow calculation of a more accurate value of bulk density, 1.90 +/- 0.1 g cm-3. This is significantly lower than the density of meteoritic analogs to Phobos' surface, suggesting a porous interior perhaps containing interstitial ice.

Astronomy↗