Nitrogen reduction under hydrothermal vent conditions: implications for the prebiotic synthesis of C-H-O-N compounds

Dinitrogen is reduced in dilute hydrogen sulfide (H2S) solutions to ammonium at 120 degrees C. Experiments with dissolved dinitrogen (partial pressure 50 bar) in a 12 x 10(-3) mol/L H2S(aq) solution yield approximately 10(-5) mol/L NH4+ within 2-7 days. These yields are consistent with the equilibrium NH4+ concentration for the N-S-H system under these conditions. The formation of ammonium is catalyzed by the presence of freshly precipitated iron monosulfide. These results indicate that dinitrogen can be reduced at moderate temperatures in hydrothermal vent systems. Abiotic nitrogen reduction could have taken place within primordial hydrothermal vents, supplying some ammonia for the synthesis of C-H-O-N compounds via abiotic processes. The yield of ammonia via dinitrogen reduction by hydrogen sulfide, however, is so low that it is doubtful this process could have produced enough ammonia to sustain prebiotic hydrothermal synthesis of C-H-O-N compounds in or around vent systems.     

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.     

Abiotic nitrogen fixation on terrestrial planets: reduction of NO to ammonia by FeS

Understanding the abiotic fixation of nitrogen and how such fixation can be a supply of prebiotic nitrogen is critical for understanding both the planetary evolution of, and the potential origin of life on, terrestrial planets. As nitrogen is a biochemically essential element, sources of biochemically accessible nitrogen, especially reduced nitrogen, are critical to prebiotic chemistry and the origin of life. Loss of atmospheric nitrogen can result in loss of the ability to sustain liquid water on a planetary surface, which would impact planetary habitability and hydrological processes that shape the surface. It is known that NO can be photochemically converted through a chain of reactions to form nitrate and nitrite, which can be subsequently reduced to ammonia. Here, we show that NO can also be directly reduced, by FeS, to ammonia. In addition to removing nitrogen from the atmosphere, this reaction is particularly important as a source of reduced nitrogen on an early terrestrial planet. By converting NO directly to ammonia in a single step, ammonia is formed with a higher product yield (~50%) than would be possible through the formation of nitrate/nitrite and subsequent conversion to ammonia. In conjunction with the reduction of NO, there is also a catalytic disproportionation at the mineral surface that converts NO to NO? and N?O. The NO? is then converted to ammonia, while the N?O is released back in the gas phase, which provides an abiotic source of nitrous oxide.     

Prebiotic significance of extraterrestrial ice photochemistry: detection of hydantoin in organic residues

The delivery of extraterrestrial organic materials to primitive Earth from meteorites or micrometeorites has long been postulated to be one of the origins of the prebiotic molecules involved in the subsequent apparition of life. Here, we report on experiments in which vacuum UV photo-irradiation of interstellar/circumstellar ice analogues containing H(2)O, CH(3)OH, and NH(3) led to the production of several molecules of prebiotic interest. These were recovered at room temperature in the semi-refractory, water-soluble residues after evaporation of the ice. In particular, we detected small quantities of hydantoin (2,4-imidazolidinedione), a species suspected to play an important role in the formation of poly- and oligopeptides. In addition, hydantoin is known to form under extraterrestrial, abiotic conditions, since it has been detected, along with various other derivatives, in the soluble part of organic matter of primitive carbonaceous meteorites. This result, together with other related experiments reported recently, points to the potential importance of the photochemistry of interstellar "dirty" ices in the formation of organics in Solar System materials. Such molecules could then have been delivered to the surface of primitive Earth, as well as other telluric (exo-) planets, to help trigger first prebiotic reactions with the capacity to lead to some form of primitive biomolecular activity.     

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.     

Biomarker response to galactic cosmic ray-induced NOx and the methane greenhouse effect in the atmosphere of an Earth-like planet orbiting an M dwarf star

Planets orbiting in the habitable zone of M dwarf stars are subject to high levels of galactic cosmic rays (GCRs), which produce nitrogen oxides (NOx) in Earth-like atmospheres. We investigate to what extent these NO(Mx) species may modify biomarker compounds such as ozone (O3) and nitrous oxide (N2O), as well as related compounds such as water (H2O) (essential for life) and methane (CH4) (which has both abiotic and biotic sources). Our model results suggest that such signals are robust, changing in the M star world atmospheric column due to GCR NOx effects by up to 20% compared to an M star run without GCR effects, and can therefore survive at least the effects of GCRs. We have not, however, investigated stellar cosmic rays here. CH4 levels are about 10 times higher on M star worlds than on Earth because of a lowering in hydroxyl (OH) in response to changes in the ultraviolet. The higher levels of CH4 are less than reported in previous studies. This difference arose partly because we used different biogenic input. For example, we employed 23% lower CH4 fluxes compared to those studies. Unlike on Earth, relatively modest changes in these fluxes can lead to larger changes in the concentrations of biomarker and related species on the M star world. We calculate a CH4 greenhouse heating effect of up to 4K. O3 photochemistry in terms of the smog mechanism and the catalytic loss cycles on the M star world differs considerably compared with that of Earth.     

Energy, chemical disequilibrium, and geological constraints on Europa

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.     

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.     

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.     

Meteors do not break exogenous organic molecules into high yields of diatomics

Meteoroids that dominate the Earth's extraterrestrial mass influx (50-300 microm size range) may have contributed a unique blend of exogenous organic molecules at the time of the origin of life. Such meteoroids are so large that most of their mass is ablated in the Earth's atmosphere. In the process, organic molecules are decomposed and chemically altered to molecules differently from those delivered to the Earth's surface by smaller (<50 microm) micrometeorites and larger (>10 cm) meteorites. The question addressed here is whether the organic matter in these meteoroids is fully decomposed into atoms or diatomic compounds during ablation. If not, then the ablation products made available for prebiotic organic chemistry, and perhaps early biology, might have retained some memory of their astrophysical nature. To test this hypothesis we searched for CN emission in meteor spectra in an airborne experiment during the 2001 Leonid meteor storm. We found that the meteor's light-emitting air plasma, which included products of meteor ablation, contained less than 1 CN molecule for every 30 meteoric iron atoms. This contrasts sharply with the nitrogen/iron ratio of 1:1.2 in the solid matter of comet 1P/Halley. Unless the nitrogen content or the abundance of complex organic matter in the Leonid parent body, comet 55P/Tempel-Tuttle, differs from that in comet 1P/Halley, it appears that very little of that organic nitrogen decomposes into CN molecules during meteor ablation in the rarefied flow conditions that characterize the atmospheric entry of meteoroids approximately 50 microm-10 cm in size. We propose that the organics of such meteoroids survive instead as larger compounds.     

Microorganisms metabolizing on clay grains in 3-km-deep Greenland basal ice

We have discovered > 10(8) microbial cells/cm3 attached to clay grains in the bottom 13 m of the GISP2 (Greenland Ice Sheet Project) ice core. Their concentration correlates with huge excesses of CO2 and CH4. We show that Fe-reducing bacteria produce most of the excess CO2 and methanogenic archaea produce the excess CH4. The number of attached cells per clay grain is proportional to grain perimeter rather than to area, which implies that nutrients are accessed at grain edges. We conclude that Fe-reducing microbes immobilized on clay surfaces metabolize via "shuttle" molecules that transport electrons to grain edges, where they reduce Fe(III) ions at edges to Fe(II) while organic acid ions are oxidized to CO2. Driven by the concentration gradient, electrons on Fe(II) ions at grain edges "hop" to Fe(III) ions inward in the same edges and oxidize them. The original Fe(III) ions can then attach new electrons from shuttle molecules at the edges. Our mechanism explains how Fe-reducers can reduce essentially all Fe(III) in clay minerals. We estimate that the Fe(III) in clay grains in the GISP2 silty ice can sustain Fe-reducing bacteria at the ambient temperature of -9 degrees C for approximately 10(6) years. F420 autofluorescence imaging shows that > 2.4% of the cells are methanogens, which account for the excess methane.     

真空羽流气相沉积污染初步研究

从固体表面对气体分子的作用着手分析气相羽流沉积污染的内在机理,阐述了固体表面对气体分子的物理吸附、化学吸附特性,给出吸附速率方程、脱附速率方程以及沉积速率方程,并通过区分贴壁吸附层、物理吸附层,重点研究了物理吸附层的脱附速率。选取有代表性的CO₂、NH₃、H₂O以及N₂H₄等气体,确定其物理吸附层脱附模型的参数,得到了与经验脱附率曲线较为一致的理论脱附率曲线。分析了单组元肼催化分解姿控发动机对太阳能帆板的气相沉积污染。     

Using biogenic sulfur gases as remotely detectable biosignatures on anoxic planets

We used one-dimensional photochemical and radiative transfer models to study the potential of organic sulfur compounds (CS(2), OCS, CH(3)SH, CH(3)SCH(3), and CH(3)S(2)CH(3)) to act as remotely detectable biosignatures in anoxic exoplanetary atmospheres. Concentrations of organic sulfur gases were predicted for various biogenic sulfur fluxes into anoxic atmospheres and were found to increase with decreasing UV fluxes. Dimethyl sulfide (CH(3)SCH(3), or DMS) and dimethyl disulfide (CH(3)S(2)CH(3), or DMDS) concentrations could increase to remotely detectable levels, but only in cases of extremely low UV fluxes, which may occur in the habitable zone of an inactive M dwarf. The most detectable feature of organic sulfur gases is an indirect one that results from an increase in ethane (C(2)H(6)) over that which would be predicted based on the planet's methane (CH(4)) concentration. Thus, a characterization mission could detect these organic sulfur gases-and therefore the life that produces them-if it could sufficiently quantify the ethane and methane in the exoplanet's atmosphere.     

Martian CH(4): sources, flux, and detection

Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.     

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.     

耐高温杂化有机硅树脂的合成及复合材料的高温力学性能

以一甲基三甲氧基硅烷(MTMS)和正硅酸乙酯(TEOS)为原料,甲醇为溶剂,通过溶胶—凝胶法制备出SiO2杂化有机硅树脂.借助傅立叶变换红外光谱(FT-IR)表征其高温结构变化,热失重分析(TG)研究SiO2杂化有基硅树脂的热稳定性和热降解机理.对TEOS改性甲基硅树脂/石英纤维复合材料在高温下的弯曲强度测试表明,TE...     

Necessary, but not sufficient: Raman identification of disordered carbon as a signature of ancient life

To identify microscopic particles as actual fossil material, it would be useful to have a means of unambiguously recognizing which carbonaceous deposits found in rocks are residues from once-living organisms (i.e., biogenic material). Those residues consist of many different, mostly aromatic (i.e., benzene ring-containing), C-O-H-dominated molecules, and typically are called kerogens. Raman microprobe spectroscopy can be applied to minute samples of ancient kerogens either isolated from their host rocks or in situ in thin section. The Raman spectra generated by monochromatic blue or green laser excitation (e.g., at 488, 514, 532 nm) typically show only generic spectral features indicative of discontinuous arrays of condensed benzene rings (i.e., structures referred to as "disordered carbonaceous material"). Thus, despite the complex chemistry of kerogens and the expected presence of H, O, and N, the Raman spectra typically do not show any evidence of functional groups, such as CH, CH(2), CH(3), CO, and CN. Moreover, the same kind of Raman spectral signature as is obtained from kerogens also is obtained from many other poorly ordered carbonaceous materials that arise through nonbiological processes, such as in situ heating of organic or inorganic compounds (whether or not they are of biological origin), metamorphic mobilization of preexisting carbon compounds, and high-temperature precipitation from hydrothermal solutions. Thus, neither a Raman spectrum, nor a Raman image derived from such spectra, definitively can identify a sample as "kerogen," but only as "disordered carbonaceous material." Clearly, the fact that small, opaque grains consist of disordered carbonaceous material is necessary, but not sufficient, to prove them to be residues of cellular material and, thus, biogenic.     

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.     

The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45?×?10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ?相似文献   

Approaching Mars-like geochemical conditions in the laboratory: omission of artificial buffers and reductants in a study of biogenic methane production on a smectite clay

Methanogens have not been shown to metabolize in conditions exactly analogous to those present in Mars' subsurface. In typical studies of methanogenic metabolism, nutrient-rich buffered media and reducing agents are added to the cultures in an attempt to optimize the environment for methanogen survival and growth. To study methanogens in more Mars-relevant laboratory conditions, efforts should be made to eliminate artificial media, buffers, and reducing agents from investigations of methanogenic metabolism. After preliminary work to compare methanogen viability on montmorillonite clay and JSC Mars-1 regolith simulant, a study was conducted to determine whether biological methanogenesis could occur in non-reduced, non-buffered environments containing only H(2), CO(2), montmorillonite, and the liquid fraction extracted from a montmorillonite/deionized water suspension. Biogenic methane was observed in the microenvironments despite the omission of traditional media, buffers, and reducing agents. Mean headspace methane concentration after 96 days of observation was 10.23%?±?0.64% (% vol?±?SEM, n?=?4). However, methane production was severely decreased with respect to reduced, buffered microenvironments (Day 28: 31.98%?±?0.19%, n?=?3). Analysis of results and comparison to previous work indicate that montmorillonite clay has a strong ability to supply micronutrients necessary for methanogenic metabolism, and the liquid fraction from a montmorillonite/deionized water slurry can successfully be used as an alternative to reduced and buffered nutritive media in Mars-relevant studies of methanogenic metabolism.