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   

Titan and exobiological aspects of the Cassini-Huygens mission

Titan, the largest satellite of Saturn, has a dense N2-CH4 atmosphere rich in organic compounds, both in gas and in aerosol phases. Its surface is probably covered by oceans of liquid methane-ethane mixtures, with many dissolved organics. This quasi planet appears as a natural laboratory to study chemical evolution toward complex organic systems in a planetary environment over a long time scale. With the Cassini-Huygens mission NASA and ESA will jointly send an orbiter (Cassini) around Saturn and a probe (Huygens) in the atmosphere of Titan. This mission, currently planned to be launched in 1996-1997 for a Saturn - Titan arrival in 2004, offers a unique opportunity to study in detail extra-terrestrial organic processes. Consequently, it has important implications in the field of exobiology and the origins of life.     

Potential climatic impact of organic haze on early Earth

We have explored the direct and indirect radiative effects on climate of organic particles likely to have been present on early Earth by measuring their hygroscopicity and cloud nucleating ability. The early Earth analog aerosol particles were generated via ultraviolet photolysis of an early Earth analog gas mixture, which was designed to mimic possible atmospheric conditions before the rise of oxygen. An analog aerosol for the present-day atmosphere of Saturn's moon Titan was tested for comparison. We exposed the early Earth aerosol to a range of relative humidities (RHs). Water uptake onto the aerosol was observed to occur over the entire RH range tested (RH=80-87%). To translate our measurements of hygroscopicity over a specific range of RHs into their water uptake ability at any RH < 100% and into their ability to act as cloud condensation nuclei (CCN) at RH > 100%, we relied on the hygroscopicity parameter κ, developed by Petters and Kreidenweis. We retrieved κ=0.22?±0.12 for the early Earth aerosol, which indicates that the humidified aerosol (RH < 100 %) could have contributed to a larger antigreenhouse effect on the early Earth atmosphere than previously modeled with dry aerosol. Such effects would have been of significance in regions where the humidity was larger than 50%, because such high humidities are needed for significant amounts of water to be on the aerosol. Additionally, Earth organic aerosol particles could have activated into CCN at reasonable-and even low-water-vapor supersaturations (RH > 100%). In regions where the haze was dominant, it is expected that low particle concentrations, once activated into cloud droplets, would have created short-lived, optically thin clouds. Such clouds, if predominant on early Earth, would have had a lower albedo than clouds today, thereby warming the planet relative to current-day clouds.     

The PROCESS experiment: exposure of amino acids in the EXPOSE-E experiment on the international space station and in laboratory simulations

To understand the chemical behavior of organic molecules in the space environment, amino acids and a dipeptide in pure form and embedded in meteorite powder were exposed in the PROCESS experiment in the EXPOSE-E facility mounted on the European Technology Exposure Facility (EuTEF) platform on board the International Space Station (ISS). After exposure to space conditions for 18 months, the samples were returned to Earth and analyzed in the laboratory for reactions caused by solar UV and cosmic radiation. Chemical degradation and possible racemization and oligomerization, the main reactions caused by photochemistry in the vacuum ultraviolet domain (VUV, wavelength range 100-200?nm for photon energy from 6.2 to 12.4?eV) were examined in particular. The molecules were extracted and derivatized by silylation and analyzed by gas chromatograph coupled to a mass spectrometer (GC-MS) to quantify the rate of the degradation of the compounds. Laboratory exposure in several wavelength ranges from UV to VUV was carried out in parallel in the Cologne Deutsches Zentrum für Luft- und Raumfahrt (DLR) Center and Centre de biophysique moléculaire (CBM) laboratories. The results show that resistance to irradiation is a function of the chemical nature of the exposed molecules and the wavelengths of the UV light. The most altered compounds were the dipeptide, aspartic acid, and aminobutyric acid. The most resistant were alanine, valine, glycine, and aminoisobutyric acid. Our results also demonstrate the protective effect of meteorite powder, which reemphasizes the importance of exogenic contribution to the inventory of prebiotic organics on early Earth.     

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.     

Ozone concentrations and ultraviolet fluxes on Earth-like planets around other stars

Coupled radiative-convective/photochemical modeling was performed for Earth-like planets orbiting different types of stars (the Sun as a G2V, an F2V, and a K2V star). O(2) concentrations between 1 and 10(-5) times the present atmospheric level (PAL) were simulated. The results were used to calculate visible/near-IR and thermal-IR spectra, along with surface UV fluxes and relative dose rates for erythema and DNA damage. For the spectral resolution and sensitivity currently planned for the first generation of terrestrial planet detection and characterization missions, we find that O(2) should be observable remotely in the visible for atmospheres containing at least 10(-2) PAL of O(2). O(3) should be visible in the thermal-IR for atmospheres containing at least 10(-3) PAL of O(2). CH(4) is not expected to be observable in 1 PAL O(2) atmospheres like that of modern Earth, but it might be observable at thermal-IR wavelengths in "mid-Proterozoic-type" atmospheres containing approximately 10(-1) PAL of O(2). Thus, the simultaneous detection of both O(3) and CH(4) - considered to be a reliable indication of life - is within the realm of possibility. High-O(2) planets orbiting K2V and F2V stars are both better protected from surface UV radiation than is modern Earth. For the F2V case the high intrinsic UV luminosity of the star is more than offset by the much thicker ozone layer. At O(2) levels below approximately 10(-2) PAL, planets around all three types of stars are subject to high surface UV fluxes, with the F2V planet exhibiting the most biologically dangerous radiation environment. Thus, while advanced life is theoretically possible on high-O(2) planets around F stars, it is not obvious that it would evolve as it did on Earth.     

氧化亚氮双组元发动机热力性能计算分析

对绿色推进剂N2O,H2,CH3OH,C2H5OH,CH4,C2H6,C2H4,C2H2,C3H8及C3H6的物性进行了全面比较,并采用吉布斯最小自由能法对9种氧化亚氮双组元推进剂组合的热力性能展开全面计算及分析。N2O/H2组合由于其最低的燃气平均摩尔质量而具有最高的比冲;N2O/C2H2组合由于C2H2很高的标准生成焓其燃烧温度可高达3823 K;碳氢燃料在余氧系数α<0.4富燃工况下燃气中含有固碳颗粒,且摩尔含量随着α的降低而急剧升高,喷管出口处可高达35%～40%;N2O/C3H8和N2O/C3H6组合拥有很好的空间应用物性和较高的热力性能,在压比pc:pe=70 atm:1 atm工况下平衡流比冲分别为2 639 m/s和2 656 m/s,具有很好的应用前景。     

Titan aerosol analogues: analysis of the nonvolatile tholins

Laboratory experiments that produced tholins in a simulated Titan atmosphere were conducted. We report the first systematic analyses of these compounds using Fourier-transform ion cyclotron resonance mass spectrometry. The findings suggest surprising simplicity and nonrandomness in the mass distribution and regularity in species clusters. The degree of unsaturation generally increased with increasing molecular weight in a predictable fashion, and nitrogen is proposed as the dominant carrier of unsaturation. In detected compounds with a general formula of C(x)H(y)N(z), the carbon to nitrogen ratio (x/z) varied only slightly within a narrow limit, and decreased with increasing molecular weights. These compounds are of potential prebiotic interest since they sediment to the surface of Titan, and would dissolve readily in transient aqueous pools that might be generated from time to time by impacts and volcanic     

The effect of a strong stellar flare on the atmospheric chemistry of an earth-like planet orbiting an M dwarf

Main sequence M stars pose an interesting problem for astrobiology: their abundance in our galaxy makes them likely targets in the hunt for habitable planets, but their strong chromospheric activity produces high-energy radiation and charged particles that may be detrimental to life. We studied the impact of the 1985 April 12 flare from the M dwarf AD Leonis (AD Leo), simulating the effects from both UV radiation and protons on the atmospheric chemistry of a hypothetical, Earth-like planet located within its habitable zone. Based on observations of solar proton events and the Neupert effect, we estimated a proton flux associated with the flare of 5.9?×?10? protons cm?2 sr?1 s?1 for particles with energies >10?MeV. Then we calculated the abundance of nitrogen oxides produced by the flare by scaling the production of these compounds during a large solar proton event called the Carrington event. The simulations were performed with a 1-D photochemical model coupled to a 1-D radiative/convective model. Our results indicate that the UV radiation emitted during the flare does not produce a significant change in the ozone column depth of the planet. When the action of protons is included, the ozone depletion reaches a maximum of 94% two years after the flare for a planet with no magnetic field. At the peak of the flare, the calculated UV fluxes that reach the surface, in the wavelength ranges that are damaging for life, exceed those received on Earth during less than 100?s. Therefore, flares may not present a direct hazard for life on the surface of an orbiting habitable planet. Given that AD Leo is one of the most magnetically active M dwarfs known, this conclusion should apply to planets around other M dwarfs with lower levels of chromospheric activity.     

Rate measurements of the hydrolysis of complex organic macromolecules in cold aqueous solutions: implications for prebiotic chemistry on the early Earth and Titan

Organic macromolecules ("complex tholins") were synthesized from a 0.95 N(2)/0.05 CH(4) atmosphere in a high-voltage AC flow discharge reactor. When placed in liquid water, specific water soluble compounds in the macromolecules demonstrated Arrhenius type first order kinetics between 273 and 313 K and produced oxygenated organic species with activation energies in the range of approximately 60+/-10 kJ mol(-1). These reactions displayed half lives between 0.3 and 17 days at 273 K. Oxygen incorporation into such materials--a necessary step toward the formation of biological molecules--is therefore fast compared to processes that occur on geologic timescales, which include the freezing of impact melt pools and possible cryovolcanic sites on Saturn's organic-rich moon Titan.     

Photochemical synthesis of citric acid cycle intermediates based on titanium dioxide

The emergence of the citric acid cycle is one of the most remarkable occurrences with regard to understanding the origin and evolution of metabolic pathways. Although the chemical steps of the cycle are preserved intact throughout nature, diverse organisms make wide use of its chemistry, and in some cases organisms use only a selected portion of the cycle. However, the origins of this cycle would have arisen in the more primitive anaerobic organism or even back in the proto-metabolism, which likely arose spontaneously under favorable prebiotic chemical conditions. In this context, we report that UV irradiation of formamide in the presence of titanium dioxide afforded 6 of the 11 carboxylic acid intermediates of the reductive version of the citric acid cycle. Since this cycle is the central metabolic pathway of contemporary biology, this report highlights the role of photochemical processes in the origin of the metabolic apparatus.     

Mass-independent fractionation of sulfur isotopes in Archean sediments: strong evidence for an anoxic Archean atmosphere

Mass-independent fractionation (MIF) of sulfur isotopes has been reported in sediments of Archean and Early Proterozoic Age (> 2.3 Ga) but not in younger rocks. The only fractionation mechanism that is consistent with the data on all four sulfur isotopes involves atmospheric photochemical reactions such as SO2 photolysis. We have used a one-dimensional photochemical model to investigate how the isotopic fractionation produced during SO2 photolysis would have been transferred to other gaseous and particulate sulfur-bearing species in both low-O2 and high-O2 atmospheres. We show that in atmospheres with O2 concentrations < 10(-5) times the present atmospheric level (PAL), sulfur would have been removed from the atmosphere in a variety of different oxidation states, each of which would have had its own distinct isotopic signature. By contrast, in atmospheres with O2 concentrations > or = 10(-5) PAL, all sulfur-bearing species would have passed through the oceanic sulfate reservoir before being incorporated into sediments, so any signature of MIF would have been lost. We conclude that the atmospheric O2 concentration must have been < 10(-5) PAL prior to 2.3 Ga.     

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.     

The PROCESS experiment: an astrochemistry laboratory for solid and gaseous organic samples in low-earth orbit

The PROCESS (PRebiotic Organic ChEmistry on the Space Station) experiment was part of the EXPOSE-E payload outside the European Columbus module of the International Space Station from February 2008 to August 2009. During this interval, organic samples were exposed to space conditions to simulate their evolution in various astrophysical environments. The samples used represent organic species related to the evolution of organic matter on the small bodies of the Solar System (carbonaceous asteroids and comets), the photolysis of methane in the atmosphere of Titan, and the search for organic matter at the surface of Mars. This paper describes the hardware developed for this experiment as well as the results for the glycine solid-phase samples and the gas-phase samples that were used with regard to the atmosphere of Titan. Lessons learned from this experiment are also presented for future low-Earth orbit astrochemistry investigations.     

Microbial life in a liquid asphalt desert

Pitch Lake in Trinidad and Tobago is a natural asphalt reservoir nourished by pitch seepage, a form of petroleum that consists of mostly asphaltines, from the surrounding oil-rich region. During upward seepage, pitch mixes with mud and gases under high pressure, and the lighter portion evaporates or is volatilized, which produces a liquid asphalt residue characterized by low water activity, recalcitrant carbon substrates, and noxious chemical compounds. An active microbial community of archaea and bacteria, many of them novel strains (particularly from the new Tar ARC groups), totaling a biomass of up to 10(7) cells per gram, was found to inhabit the liquid hydrocarbon matrix of Pitch Lake. Geochemical and molecular taxonomic approaches revealed diverse, novel, and deeply branching microbial lineages with the potential to mediate anaerobic hydrocarbon degradation processes in different parts of the asphalt column. In addition, we found markers for archaeal methane metabolism and specific gene sequences affiliated with facultative and obligate anaerobic sulfur- and nitrite-oxidizing bacteria. The microbial diversity at Pitch Lake was found to be unique when compared to microbial communities analyzed at other hydrocarbon-rich environments, which included Rancho Le Brea, a natural asphalt environment in California, USA, and an oil well and a mud volcano in Trinidad and Tobago, among other sites. These results open a window into the microbial ecology and biogeochemistry of recalcitrant hydrocarbon matrices and establish the site as a terrestrial analogue for modeling the biotic potential of hydrocarbon lakes such as those found on Saturn's largest moon Titan.     

Formation routes of interstellar glycine involving carboxylic acids: possible favoritism between gas and solid phase

Despite the extensive search for glycine (NH?CH?COOH) and other amino acids in molecular clouds associated with star-forming regions, only upper limits have been derived from radio observations. Nevertheless, two of glycine's precursors, formic acid and acetic acid, have been abundantly detected. Although both precursors may lead to glycine formation, the efficiency of reaction depends on their abundance and survival in the presence of a radiation field. These facts could promote some favoritism in the reaction pathways in the gas phase and solid phase (ice). Glycine and these two simplest carboxylic acids are found in many meteorites. Recently, glycine was also observed in cometary samples returned by the Stardust space probe. The goal of this work was to perform theoretical calculations for several interstellar reactions involving the simplest carboxylic acids as well as the carboxyl radical (COOH) in both gas and solid (ice) phase to understand which reactions could be the most favorable to produce glycine in interstellar regions fully illuminated by soft X-rays and UV, such as star-forming regions. The calculations were performed at four different levels for the gas phase (B3LYP/6-31G*, B3LYP/6-31++G**, MP2/6-31G*, and MP2/6-31++G**) and at MP2/6-31++G** level for the solid phase (ice). The current two-body reactions (thermochemical calculation) were combined with previous experimental data on the photodissociation of carboxylic acids to promote possible favoritism for glycine formation in the scenario involving formic and acetic acid in both gas and solid phase. Given that formic acid is destroyed more in the gas phase by soft X-rays than acetic acid is, we suggest that in the gas phase the most favorable reactions are acetic acid with NH or NH?OH. Another possible reaction involves NH?CH? and COOH, one of the most-produced radicals from the photodissociation of acetic acid. In the solid phase, we suggest that the reactions of formic acid with NH?CH or NH?CH?OH are the most favorable from the thermochemical point of view.     

Haze aerosols in the atmosphere of early Earth: manna from heaven

An organic haze layer in the upper atmosphere of Titan plays a crucial role in the atmospheric composition and climate of that moon. Such a haze layer may also have existed on the early Earth, providing an ultraviolet shield for greenhouse gases needed to warm the planet enough for life to arise and evolve. Despite the implications of such a haze layer, little is known about the organic material produced under early Earth conditions when both CO(2) and CH(4) may have been abundant in the atmosphere. For the first time, we experimentally demonstrate that organic haze can be generated in different CH(4)/CO(2) ratios. Here, we show that haze aerosols are able to form at CH(4) mixing ratios of 1,000 ppmv, a level likely to be present on early Earth. In addition, we find that organic hazes will form at C/O ratios as low as 0.6, which is lower than the predicted value of unity. We also show that as the C/O ratio decreases, the organic particles produced are more oxidized and contain biologically labile compounds. After life arose, the haze may thus have provided food for biota.     

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.     

Photochemical initiation of gaseous detonations

Direct initiation of detonations in gaseous mixtures of C₂H₂-O₂, H₂-O₂ and H₂-Cl₂ in the pressure range of 10–150 torr using flash photolysis was studied. Similar to blast initiation using a concentrated powerful energy source, it was found that for photochemical initiation, there exists a certain threshold of flash intensity and energy for each mixture at any given initial pressure and composition below which a deflagration is formed. At the critical threshold, however, a fully developed detonation is rapidly formed in the immediate vicinity of the window of incident UV radiation. However, at super critical flash energies, the amplitude of the detonation formed decreases and combustion of the entire irradiated volume approaches a constant volume explosion. It was found that photo-chemical initiation requires both a certain minimum peak value of the free radical concentration generated by the photo-dissociation as well as an appropriate gradient of this free radical distribution. The minimum peak radical concentration permits rapid reaction rates for the generation of strong pressure waves, while the gradient is necessary for the amplification of the shock waves to a detonation. If the gradient is absent and the free radicals are uniformly distributed in the mixture, then the entire volume simply explodes as in a constant volume process. The present study reveals that the mechanism of photochemical initiation is one of proper temporal synchronization of the chemical energy release to the shock wave as it propagates through the mixture. In analogy to the LASER, the term SWACER is introduced to represent this mechanism of Shock Wave Amplication by Coherent Energy Release. There are strong indications that this SWACER mechanism is universal and plays the main role in the formation of detonations whenever a powerful concentrated external source is not used to generate a strong shock wave in the explosive.     

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.