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   

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.     

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.     

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.     

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.     

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.     

Biosignatures of early earths

A major goal of NASA's Origins Program is to find habitable planets around other stars and determine which might harbor life. Determining whether or not an extrasolar planet harbors life requires an understanding of what spectral features (i.e., biosignatures) might result from life's presence. Consideration of potential biosignatures has tended to focus on spectral features of gases in Earth's modern atmosphere, particularly ozone, the photolytic product of biogenically produced molecular oxygen. But life existed on Earth for about 1(1/2) billion years before the buildup of atmospheric oxygen. Inferred characteristics of Earth's earliest biosphere and studies of modern microbial ecosystems that share some of those characteristics suggest that organosulfur compounds, particularly methanethiol (CH(3)SH, the sulfur analog of methanol), may have been biogenic products on early Earth. Similar production could take place on extrasolar Earth-like planets whose biota share functional chemical characteristics with Earth life. Since methanethiol and related organosulfur compounds (as well as carbon dioxide) absorb at wavelengths near or overlapping the 9.6-microm band of ozone, there is potential ambiguity in interpreting a feature around this wavelength in an extrasolar planet spectrum.     

A sulfur-based survival strategy for putative phototrophic life in the venusian atmosphere

Several observations indicate that the cloud deck of the venusian atmosphere may provide a plausible refuge for microbial life. Having originated in a hot proto-ocean or been brought in by meteorites from Earth (or Mars), early life on Venus could have adapted to a dry, acidic atmospheric niche as the warming planet lost its oceans. The greatest obstacle for the survival of any organism in this niche may be high doses of ultraviolet (UV) radiation. Here we make the argument that such an organism may utilize sulfur allotropes present in the venusian atmosphere, particularly S(8), as a UV sunscreen, as an energy-converting pigment, or as a means for converting UV light to lower frequencies that can be used for photosynthesis. Thus, life could exist today in the clouds of Venus.     

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.     

Mutagenesis in bacterial spores exposed to space and simulated martian conditions: data from the EXPOSE-E spaceflight experiment PROTECT

As part of the PROTECT experiment of the EXPOSE-E mission on board the International Space Station (ISS), the mutagenic efficiency of space was studied in spores of Bacillus subtilis 168. After 1.5 years' exposure to selected parameters of outer space or simulated martian conditions, the rates of induced mutations to rifampicin resistance (Rif(R)) and sporulation deficiency (Spo(-)) were quantified. In all flight samples, both mutations, Rif(R) and Spo(-), were induced and their rates increased by several orders of magnitude. Extraterrestrial solar UV radiation (>110?nm) as well as simulated martian UV radiation (>200?nm) led to the most pronounced increase (up to nearly 4 orders of magnitude); however, mutations were also induced in flight samples shielded from insolation, which were exposed to the same conditions except solar irradiation. Nucleotide sequencing located the Rif(R) mutations in the rpoB gene encoding the β-subunit of RNA polymerase. Mutations isolated from flight and parallel mission ground reference (MGR) samples were exclusively localized to Cluster I. The 21 Rif(R) mutations isolated from the flight experiment showed all a C to T transition and were all localized to one hotspot: H482Y. In mutants isolated from the MGR, the spectrum was wider with predicted amino acid changes at residues Q469K/L/R, H482D/P/R/Y, and S487L. The data show the unique mutagenic power of space and martian surface conditions as a consequence of DNA injuries induced by solar UV radiation and space vacuum or the low pressure of Mars.     

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.     

Coronal mass ejection (CME) activity of low mass M stars as an important factor for the habitability of terrestrial exoplanets. II. CME-induced ion pick up of Earth-like exoplanets in close-in habitable zones

Atmospheric erosion of CO2-rich Earth-size exoplanets due to coronal mass ejection (CME)-induced ion pick up within close-in habitable zones of active M-type dwarf stars is investigated. Since M stars are active at the X-ray and extreme ultraviolet radiation (XUV) wave-lengths over long periods of time, we have applied a thermal balance model at various XUV flux input values for simulating the thermospheric heating by photodissociation and ionization processes due to exothermic chemical reactions and cooling by the CO2 infrared radiation in the 15 microm band. Our study shows that intense XUV radiation of active M stars results in atmospheric expansion and extended exospheres. Using thermospheric neutral and ion densities calculated for various XUV fluxes, we applied a numerical test particle model for simulation of atmospheric ion pick up loss from an extended exosphere arising from its interaction with expected minimum and maximum CME plasma flows. Our results indicate that the Earth-like exoplanets that have no, or weak, magnetic moments may lose tens to hundreds of bars of atmospheric pressure, or even their whole atmospheres due to the CME-induced O ion pick up at orbital distances 相似文献   

Radiolytic hydrogen and microbial respiration in subsurface sediments

Radiolysis of water may provide a continuous flux of an electron donor (molecular hydrogen) to subsurface microbial communities. We assessed the significance of this process in anoxic marine sediments by comparing calculated radiolytic H(2) production rates to estimates of net (organic-fueled) respiration at several Ocean Drilling Program (ODP) Leg 201 sites. Radiolytic H(2) yield calculations are based on abundances of radioactive elements (uranium, thorium, and potassium), porosity, grain density, and a model of water radiolysis. Net respiration estimates are based on fluxes of dissolved electron acceptors and their products. Comparison of radiolytic H(2) yields and respiration at multiple sites suggests that radiolysis gains importance as an electron donor source as net respiration and organic carbon content decrease. Our results suggest that radiolytic production of H(2) may fuel 10% of the metabolic respiration at the Leg 201 site where organic-fueled respiration is lowest (ODP Site 1231). In sediments with even lower rates of organic-fueled respiration, water radiolysis may be the principal source of electron donors. Marine sedimentary ecosystems may be useful models for non-photosynthetic ecosystems on early Earth and on other planets and moons, such as Mars and Europa.     

Nitrogen incorporation in CH(4)-N(2) photochemical aerosol produced by far ultraviolet irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ<120?nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120-200?nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We examined the chemical properties of photochemical aerosol produced at far UV wavelengths, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH(4)/N(2) photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N(2) in the irradiated gas. The aerosol mass greatly decreases when N(2) is removed, which indicates that N(2) plays a major role in aerosol production. Because direct dissociation of N(2) is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N(2) must occur via another pathway. Any chemical activation of N(2) at wavelengths >120?nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH(4) photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets.     

An inexpensive apparatus for growing photosynthetic microorganisms in exotic atmospheres

Given the need for a light source, cyanobacteria and other photosynthetic microorganisms can be difficult and expensive to grow in large quantities. Lighted growth chambers and incubators typically cost 50-100% more than standard microbiological incubators. Self-shading of cells in liquid cultures prevents the growth of dense suspensions. Growing liquid cultures on a shaker table or lighted shaker incubator achieves greater cell densities, but adds considerably to the cost. For experiments in which gases other than air are required, the cost for conventional incubators increases even more. We describe an apparatus for growing photosynthetic organisms in exotic atmospheres that can be built relatively inexpensively (approximately 100 dollars U.S.) using parts available from typical hardware or department stores (e.g., Wal-mart or K-mart). The apparatus uses microfiltered air (or other gases) to aerate, agitate, and mix liquid cultures, thus achieving very high cell densities (A750 > 3). Because gases are delivered to individual culture tubes, a variety of gas mixes can be used without the need for enclosed chambers. The apparatus works with liquid cultures of unicellular and filamentous species, and also works with agar slants.     

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.     

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.     

The potential feasibility of chlorinic photosynthesis on exoplanets

The modern search for life-bearing exoplanets emphasizes the potential detection of O(2) and O(3) absorption spectra in exoplanetary atmospheres as ideal signatures of biology. However, oxygenic photosynthesis may not arise ubiquitously in exoplanetary biospheres. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This paper defines chlorinic photosynthesis (CPS) as biologically mediated photolytic oxidation of aqueous Cl(-) to form halocarbon or dihalogen products, coupled with CO(2) assimilation. This hypothetical metabolism appears to be feasible energetically, physically, and geochemically, and could potentially develop under conditions that approximate the terrestrial Archean. It is hypothesized that an exoplanetary biosphere in which chlorinic photosynthesis dominates primary production would tend to evolve a strongly oxidizing, halogen-enriched atmosphere over geologic time. It is recommended that astronomical observations of exoplanetary outgoing thermal emission spectra consider signs of halogenated chemical species as likely indicators of the presence of a chlorinic biosphere. Planets that favor the evolution of CPS would probably receive equivalent or greater surface UV flux than is produced by the Sun, which would promote stronger abiotic UV photolysis of aqueous halides than occurred during Earth's Archean era and impose stronger evolutionary selection pressures on endemic life to accommodate and utilize halogenated compounds. Ocean-bearing planets of stars with metallicities equivalent to, or greater than, the Sun should especially favor the evolution of chlorinic biospheres because of the higher relative seawater abundances of Cl, Br, and I such planets would tend to host. Directed searches for chlorinic biospheres should probably focus on G0-G2, F, and A spectral class stars that have bulk metallicities of +0.0 Dex or greater.     

Biosignatures from Earth-like planets around M dwarfs

Coupled one-dimensional photochemical-climate calculations have been performed for hypothetical Earth-like planets around M dwarfs. Visible/near-infrared and thermal-infrared synthetic spectra of these planets were generated to determine which biosignature gases might be observed by a future, space-based telescope. Our star sample included two observed active M dwarfs-AD Leo and GJ 643-and three quiescent model stars. The spectral distribution of these stars in the ultraviolet generates a different photochemistry on these planets. As a result, the biogenic gases CH4, N2O, and CH3Cl have substantially longer lifetimes and higher mixing ratios than on Earth, making them potentially observable by space-based telescopes. On the active M-star planets, an ozone layer similar to Earth's was developed that resulted in a spectroscopic signature comparable to the terrestrial one. The simultaneous detection of O2 (or O3) and a reduced gas in a planet's atmosphere has been suggested as strong evidence for life. Planets circling M stars may be good locations to search for such evidence.     

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.