The catalytic potential of cosmic dust: implications for prebiotic chemistry in the solar nebula and other protoplanetary systems

The synthesis of important prebiotic molecules is fundamentally reliant on basic starting ingredients: water, organic species [e.g., methane (CH(4))], and reduced nitrogen compounds [e.g., ammonia (NH(3)), methyl cyanide (CH(3)CN) etc.]. However, modern studies conclude that the primordial Earth's atmosphere was too rich in CO, CO(2), and water to permit efficient synthesis of such reduced molecules as envisioned by the classic Miller-Urey experiment. Other proposed sources of terrestrial nitrogen reduction, like those within submarine vent systems, also seem to be inadequate sources of chemically reduced C-H-O-N compounds. Here, we demonstrate that nebular dust analogs have impressive catalytic properties for synthesizing prebiotic molecules. Using a catalyst analogous to nebular iron silicate condensate, at temperatures ranging from 500K to 900K, we catalyzed both the Fischer-Tropsch conversion of CO and H(2) to methane and water, and the corresponding Haber-Bosch synthesis of ammonia from N(2) and H(2). Remarkably, when CO, N(2), and H(2) were allowed to react simultaneously, these syntheses also yielded nitrogen-containing organics such as methyl amine (CH(3)NH(2)), acetonitrile (CH(3)CN), and N-methyl methylene imine (H(3)CNCH(2)). A fundamental consequence of this work for astrobiology is the potential for a natural chemical pathway to produce complex chemical building blocks of life throughout our own Solar System and beyond.     

Sulfur-oxidizing chemolithotrophic proteobacteria dominate the microbiota in high arctic thermal springs on Svalbard

The thermal springs Trollosen and Fisosen, located on the High Arctic archipelago Svalbard, discharge saline groundwaters rich in hydrogen sulfide and ammonium through a thick layer of permafrost. Large amounts of biomass that consist of filamentous microorganisms containing sulfur granules, as analyzed with energy dispersive X-ray analysis, were found in the outflow. Prokaryotic 16S rRNA gene libraries and quantitative polymerase chain reaction (qPCR) analyses reported bacteria of the γ- and ?-proteobacterial classes as the dominant organisms in the filaments and the planktonic fractions, closely related to known chemolithoautotrophic sulfur oxidizers (Thiotrix and Sulfurovum). Archaea comprised ～1% of the microbial community, with the majority of sequences affiliated with the Thaumarchaeota. Archaeal and bacterial genes coding for a subunit of the enzyme ammonia monooxygenase (amoA) were detected, as well as 16S?rRNA genes of Nitrospira, all of which is indicative of potential complete nitrification in both springs. 16S rRNA sequences related to methanogens and methanotrophs were detected as well. This study provides evidence that the microbial communities in Trollosen and Fisosen are sustained by chemolithotrophy, mainly through the oxidation of reduced sulfur compounds, and that ammonium and methane might be minor, additional sources of energy and carbon.     

Temporal changes in fluid chemistry and energy profiles in the vulcano island hydrothermal system

In June 2003, the geochemical composition of geothermal fluids was determined at 9 sites in the Vulcano hydrothermal system, including sediment seeps, geothermal wells, and submarine vents. Compositional data were combined with standard state reaction properties to determine the overall Gibbs free energy (DeltaG(r) ) for 120 potential lithotrophic and heterotrophic reactions. Lithotrophic reactions in the H-O-N-S-C-Fe system were considered, and exergonic reactions yielded up to 120 kJ per mole of electrons transferred. The potential for heterotrophy was characterized by energy yields from the complete oxidation of 6 carboxylic acids- formic, acetic, propanoic, lactic, pyruvic, and succinic-with the following redox pairs: O(2)/H(2)O, SO(4) (2)/H(2)S, NO(3) ()/NH(4) (+), S(0)/H(2)S, and Fe(3)O(4)/Fe(2+). Heterotrophic reactions yielded 6-111 kJ/mol e(). Energy yields from both lithotrophic and heterotrophic reactions were highly dependent on the terminal electron acceptor (TEA); reactions with O(2) yielded the most energy, followed by those with NO(3) (), Fe(III), SO(4) (2), and S(0). When only reactions with complete TEA reduction were included, the exergonic lithotrophic reactions followed a similar electron tower. Spatial variability in DeltaG(r) was significant for iron redox reactions, owing largely to the wide range in Fe(2+) and H(+) concentrations. Energy yields were compared to those obtained for samples collected in June 2001. The temporal variations in geochemical composition and energy yields observed in the Vulcano hydrothermal system between 2001 and 2003 were moderate. The largest differences in DeltaG(r) over the 2 years were from iron redox reactions, due to temporal changes in the Fe(2+) and H(+) concentrations. The observed variations in fluid composition across the Vulcano hydrothermal system have the potential to influence not only microbial diversity but also the metabolic strategies of the resident microbial communities.     

Microbial diversity of Indian Ocean hydrothermal vent plumes: microbes tolerant of desiccation, peroxide exposure, and ultraviolet and gamma-irradiation

The microbial diversity of Kali chimney plumes, part of a hydrothermal vent field in the Rodriguez Triple Junction, Indian Ocean (depth approximately 2,240 m), was examined in an attempt to discover "extremotolerant" microorganisms that have evolved unique resistance capabilities to this harsh environment. Water and sediment samples were collected from the vent and from sediments located at various distances (2-20 m) away from and surrounding the chimney. Samples were screened for hypertolerant microbes that are able to withstand multiple stresses. A total of 46 isolates were selected for exposure to a number of perturbations, such as heat shock, desiccation, H(2)O(2), and ultraviolet (UV) and gamma-irradiation. The survival of Psychrobacter sp. L0S3S-03b following exposure to >1,000 J/m(2) UV(254) radiation was particularly intriguing amid a background of varying levels of resistance. Vegetative cells of this non-spore-forming microbe not only survived all of the treatments, but also exhibited a 90% lethal dose of 30 s when exposed to simulated martian UV radiation and a 100% lethal dose of 2 min when exposed to full spectrum UV, which is comparable to findings for bacterial endospores.     

Geochemical constraints on sources of metabolic energy for chemolithoautotrophy in ultramafic-hosted deep-sea hydrothermal systems

Numerical models are employed to investigate sources of chemical energy for autotrophic microbial metabolism that develop during mixing of oxidized seawater with strongly reduced fluids discharged from ultramafic-hosted hydrothermal systems on the seafloor. Hydrothermal fluids in these systems are highly enriched in H(2) and CH(4) as a result of alteration of ultramafic rocks (serpentinization) in the subsurface. Based on the availability of chemical energy sources, inferences are made about the likely metabolic diversity, relative abundance, and spatial distribution of microorganisms within ultramafic-hosted systems. Metabolic reactions involving H(2) and CH(4), particularly hydrogen oxidation, methanotrophy, sulfate reduction, and methanogenesis, represent the predominant sources of chemical energy during fluid mixing. Owing to chemical gradients that develop from fluid mixing, aerobic metabolisms are likely to predominate in low-temperature environments (<20-30 degrees C), while anaerobes will dominate higher-temperature environments. Overall, aerobic metabolic reactions can supply up to approximately 7 kJ of energy per kilogram of hydrothermal fluid, while anaerobic metabolic reactions can supply about 1 kJ, which is sufficient to support a maximum of approximately 120 mg (dry weight) of primary biomass production by aerobic organisms and approximately 20-30 mg biomass by anaerobes. The results indicate that ultramafic-hosted systems are capable of supplying about twice as much chemical energy as analogous deep-sea hydrothermal systems hosted in basaltic rocks.     

Condensation reactions and formation of amides, esters, and nitriles under hydrothermal conditions

Hydrothermal pyrolysis experiments were performed to assess condensation (dehydration) reactions to amide, ester, and nitrile functionalities from lipid precursors. Beside product formation, organic compound alteration and stability were also evaluated. Mixtures of nonadecanoic acid, hexadecanedioic acid, or hexadecanamide with water, ammonium bicarbonate, and oxalic acid were heated at 300 degrees C for 72 h. In addition, mixtures of ammonium bicarbonate and oxalic acid solutions were used to test the abiotic formation of organic nitrogen compounds at the same temperature. The resulting products were condensation compounds such as amides, nitriles, and minor quantities of N-methylalkyl amides, alkanols, and esters. Mixtures of alkyl amide in water or oxalic acid yielded mainly hydrolysis and dehydration products, and with ammonium bicarbonate and oxalic acid the yield of condensation products was enhanced. The synthesis experiments with oxalic acid and ammonium bicarbonate solutions yielded homologous series of alkyl amides, alkyl amines, alkanes, and alkanoic acids, all with no carbon number predominances. These organic nitrogen compounds are stable and survive under the elevated temperatures of hydrothermal fluids.     

Amino acids from ion-irradiated nitrile-containing ices

Solid CH(3)CN and solid H(2)O + CH(3)CN were ion irradiated near 10 K to initiate chemical reactions thought to occur in extraterrestrial ices. The infrared spectra of these samples after irradiation revealed the synthesis of new molecules. After the irradiated ices were warmed to remove volatiles, the resulting residual material was extracted and analyzed. Both unhydrolyzed and acid-hydrolyzed residues were examined by both liquid and gas chromatographic-mass spectral methods and found to contain a rich mixture of products. The unhydrolyzed samples showed HCN, NH(3), acetaldehyde (formed by reaction with background and atmospheric H(2)O), alkyamines, and numerous other compounds, but no amino acids. However, reaction products in hydrolyzed residues contained a suite of amino acids that included some found in carbonaceous chondrite meteorites. Equal amounts of D- and L-enantiomers were found for each chiral amino acid detected. Extensive use was made of (13)C-labeled CH(3)CN to confirm amino acid identifications and discriminate against possible terrestrial contaminants. The results reported here show that ices exposed to cosmic rays can yield products that, after hydrolysis, form a set of primary amino acids equal in richness to those made by other methods, such as photochemistry.     

Mineral-enhanced hydrothermal oligopeptide formation at the second time scale

Accumulation of biopolymers should have been an essential step for the emergence of life on primitive Earth. However, experimental simulations for submarine hydrothermal vent systems in which high-temperature water spouts through minerals within a short time scale have not been attempted. Here, we show that enhancement of hydrothermal oligopeptide elongation by naturally occurring minerals was successfully verified for the first time by using a mineral-mediated hydrothermal flow reactor system (MMHF). MMHF consists of a narrow tubular reactor packed with mineral particles, and the enhancement or inhibitory activities of 10 types of naturally occurring minerals were successfully evaluated for an elongation reaction from (Ala)(4) to (Ala)(5) and higher oligopeptides in the absence of condensation reagents. It was unexpected that calcite and dolomite facilitated the elongation from (Ala)(4) to (Ala)(5) and higher oligopeptides with 28% yield at pH 7, while tourmaline, galena, apatite, mica, sphalerite, quartz, chalcopyrite, and pyrite did not show enhancement activities. These facts suggest the importance of carbonate minerals for the accumulation of peptide in primitive Earth environments.     

Elucidation of an iterative process of carbon-carbon bond formation of prebiotic significance

Laboratory experiments carried out under plausible prebiotic conditions (under conditions that might have occurred at primitive deep-sea hydrothermal vents) in water and involving constituents that occur in the vicinity of submarine hydrothermal vents (e.g., CO, H(2)S, NiS) have disclosed an iterative Ni-catalyzed pathway of C-C bond formation. This pathway leads from CO to various organic molecules that comprise, notably, thiols, alkylmono- and disulfides, carboxylic acids, and related thioesters containing up to four carbon atoms. Furthermore, similar experiments with organic compounds containing various functionalities, such as thiols, carboxylic acids, thioesters, and alcohols, gave clues to the mechanisms of this novel synthetic process in which reduced metal species, in particular Ni(0), appear to be the key catalysts. Moreover, the formation of aldehydes (and ketones) as labile intermediates via a hydroformylation-related process proved to be at the core of the chain elongation process. Since this process can potentially lead to organic compounds with any chain length, it could have played a significant role in the prebiotic formation of lipidic amphiphilic molecules such as fatty acids, potential precursors of membrane constituents.     

Application of the Mars Organic Analyzer to nucleobase and amine biomarker detection

The Mars Organic Analyzer (MOA), a portable microfabricated capillary electrophoresis instrument being developed for planetary exploration, is used to analyze a wide variety of fluorescamine-labeled amine-containing biomarker compounds, including amino acids, mono and diaminoalkanes, amino sugars, nucleobases, and nucleobase degradation products. The nucleobases cytosine and adenine, which contain an exocyclic primary amine, were effectively labeled, separated, and detected at concentrations <500 nM. To test the general applicability of the MOA for biomarker detection, amino acids and mono- and diamines were extracted from bacterial cells using both hydrolysis and sublimation followed by analysis. The extrapolated limit of detection provided by the valine biomarker was approximately 4 x 10(3) cells per sample. Products of an NH(4)CN polymerization that simulate a prebiotic synthesis were also successfully isolated via sublimation and analyzed. Adenine and alanine/serine were detected with no additional sample cleanup at 120 +/- 13 microM and 4.1 +/- 1 microM, respectively, corresponding to a reaction yield of 0.04% and 0.0003%, respectively. This study demonstrates that the MOA provides sensitive detection and analysis of low levels of a wide variety of amine-containing organic compounds from both biological and abiotic sources.     

核热火箭发动机系统循环方案分析与设计

核热火箭发动机是未来实现载人火星探测的首选动力方案,其具备高比冲、大推力和长工作寿命等优点。我国在此方面研究较少,亟需开展核热推进技术理论及方法的研究。核热火箭发动机系统循环分析与设计是关键问题之一,对推进系统总体设计有重要意义。分析了3种可用于核热火箭发动机系统循环的方案特点,基于闭式膨胀循环设计了比冲为910 s ...     

Physical-chemical treatment of wastes: a way to close turnover of elements in LSS.

"Man-plants-physical-chemical unit" system designed for space stations or terrestrial ecohabitats to close steady-state mineral, water and gas exchange is proposed. The physical-chemical unit is to mineralize all inedible plant wastes and physiological human wastes (feces, urine, gray water) by electromagnetically activated hydrogen peroxide in an oxidation reactor. The final product is a mineralized solution containing all elements balanced for plants' requirements. The solution has been successfully used in experiments to grow wheat, beans and radish. The solution was reusable: the evaporated moisture was replenished by the phytotron condensate. Sodium salination of plants was precluded by evaporating reactor-mineralized urine to sodium saturation concentration to crystallize out NaCl which can be used as food for the crew. The remaining mineralized product was brought back for nutrition of plants. The gas composition of the reactor comprises O2, N2, CO2, NH3, H2. At the reactor's output hydrogen and oxygen were catalyzed into water, NH3 was converted in a water trap into NH4 and used for nutrition of plants. A special accessory at the reactor's output may produce hydrogen peroxide from intrasystem water and gas which makes possible to close gas loops between LSS components.     

Formation of nucleobases from formamide in the presence of iron oxides: implication in chemical evolution and origin of life

Simple compounds like HCN, which have one C and one N, are proposed as the probable precursors for biomonomers. Formamide, a hydrolysis product of HCN, is known as the precursor of various biologically important compounds, for example, nucleobases (purines and pyrimidines). In this paper, we report our results on the synthesis of nucleobases, adenine, cytosine, purine, 9-(hydroxyacetyl) purine, and 4(3H)-pyrimidinone from formamide, using iron oxide (hematite) and oxide hydroxides (goethite and akaganeite) as a catalyst. Goethite and hematite produced purine in higher yield. The products formed were characterized by high-performance liquid chromatography and electrospray ionization mass spectrometry techniques. Results of our study reveal that iron oxides might have worked as efficient prebiotic catalysts.     

Determination of epsomite-hexahydrite equilibria by the humidity-buffer technique at 0.1 MPa with implications for phase equilibria in the system MgSO4-H2O

Epsomite (MgSO(4).7H(2)O) and hexahydrite (MgSO(4).6H(2)O) are common minerals found in marine evaporite deposits, in saline lakes as precipitates, in weathering zones of coal and metallic deposits, in some soils and their efflorescences, and possibly on the surface of Europa as evaporite deposits. Thermodynamic properties of these two minerals reported in the literature are in poor agreement. In this study, epsomite-hexahydrite equilibria were determined along four humidity-buffer curves at 0.1 MPa and between 25 and 45 degrees C. Results obtained for the reaction epsomite = hexahydrite + H(2)O, as demonstrated by very tight reversals along each humidity buffer, can be represented by ln K(+/- 0.012) = 20.001 - 7182.07/T, where K is the equilibrium constant, and T is temperature in Kelvin. The derived standard Gibbs free energy of reaction is 10.13 +/- 0.07 kJ/mol, which is essentially the same value as that calculated from vapor pressure measurements reported in the literature. However, this value is at least 0.8 kJ/mol lower than those calculated from the data derived mostly from calorimetric measurements.     

Nucleobases and prebiotic molecules in organic residues produced from the ultraviolet photo-irradiation of pyrimidine in NH(3) and H(2)O+NH(3) ices

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases-the information subunits of DNA and RNA-are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab initio calculations have already shown that the irradiation of pyrimidine in pure H(2)O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH(3):pyrimidine and H(2)O:NH(3):pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.     

Production of oxidants by ion irradiation of water/carbon dioxide frozen mixtures

We present new experimental results on the formation of oxidants, such as hydrogen peroxide, ozone, and carbonic acid, under ion irradiation of icy mixtures of water/carbon dioxide at different ratios and temperatures (16 and 80 K). Pure water ice layers and mixtures with carbon dioxide were irradiated by 200 keV He+ ions. We found that the CO(2)/H(2)O ratio progressively decreased to a value of about 0.1, the H(2)O(2) production increased with increasing CO(2) abundance at both 16 and 80 K, and the CO and H(2)CO(3) production increased with increasing CO(2) abundance at 16 K. At 80 K, the synthesis of CO was less efficient because of the high volatility of the molecule that partially sublimed from the target. The production of carbonic acid was connected with the production of CO(3). O(3) was detected only after ion irradiation of CO(2)-rich mixtures. The experimental results are discussed with regard to the relevance they may have in the production of an energy source for a europan or a martian biosphere.     

Hydrogeologic controls on episodic H2 release from precambrian fractured rocks--energy for deep subsurface life on earth and mars

Dissolved H(2) concentrations up to the mM range and H(2) levels up to 9-58% by volume in the free gas phase are reported for groundwaters at sites in the Precambrian shields of Canada and Finland. Along with previously reported dissolved H(2) concentrations up to 7.4 mM for groundwaters from the Witwatersrand Basin, South Africa, these findings indicate that deep Precambrian Shield fracture waters contain some of the highest levels of dissolved H(2) ever reported and represent a potentially important energy-rich environment for subsurface microbial life. The delta (2)H isotope signatures of H(2) gas from Canada, Finland, and South Africa are consistent with a range of H(2)-producing water-rock reactions, depending on the geologic setting, which include both serpentinization and radiolysis. In Canada and Finland, several of the sites are in Archean greenstone belts characterized by ultramafic rocks that have under-gone serpentinization and may be ancient analogues for serpentinite-hosted gases recently reported at the Lost City Hydrothermal Field and other hydrothermal seafloor deposits. The hydrogeologically isolated nature of these fracture-controlled groundwater systems provides a mechanism whereby the products of water-rock interaction accumulate over geologic timescales, which produces correlations between high H(2) levels, abiogenic hydrocarbon signatures, and the high salinities and highly altered delta (18)O and delta (2)H values of these groundwaters. A conceptual model is presented that demonstrates how periodic opening of fractures and resultant mixing control the distribution and supply of H(2) and support a microbial community of H(2)-utilizing sulfate reducers and methanogens.     

Pyrite-induced hydrogen peroxide formation as a driving force in the evolution of photosynthetic organisms on an early earth

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.     

Genesis and preservation of a uranium-rich paleozoic epithermal system with a surface expression (Northern Flinders Ranges, South Australia): radiogenic heat driving regional hydrothermal circulation over geological timescales

The surface expressions of hydrothermal systems are prime targets for astrobiological exploration, and fossil systems on Earth provide an analogue to guide this endeavor. The Paleozoic Mt. Gee-Mt. Painter system (MGPS) in the Northern Flinders Ranges of South Australia is exceptionally well preserved and displays both a subsurface quartz sinter (boiling horizon) and remnants of aerial sinter pools that lie in near-original position. The energy source for the MGPS is not related to volcanism but to radiogenic heat produced by U-Th-K-rich host rocks. This radiogenic heat source drove hydrothermal circulation over a long period of time (hundreds of millions of years, from Permian to present), with peaks in hydrothermal activity during periods of uplift and high water supply. This process is reflected by ongoing hot spring activity along a nearby fault. The exceptional preservation of the MGPS resulted from the lack of proximal volcanism, coupled with tectonics driven by an oscillating far-field stress that resulted in episodic basement uplift. Hydrothermal activity caused the remobilization of U and rare earth elements (REE) in host rocks into (sub)economic concentrations. Radiogenic-heat-driven systems are attractive analogues for environments that can sustain life over geological times; the MGPS preserves evidence of episodic fluid flow for the past ～300 million years. During periods of reduced hydrothermal activity (e.g., limited water supply, quiet tectonics), radiolytic H(2) production has the potential to support an ecosystem indefinitely. Remote exploration for deposits similar to those at the MGPS systems can be achieved by combining hyperspectral and gamma-ray spectroscopy.