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.     

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.     

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   

Stable iron isotopes and microbial mediation in red pigmentation of the Rosso Ammonitico (mid-late Jurassic, Verona area, Italy)

The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.     

Was there a late Archean biospheric explosion?

There is a growing body of evidence which suggests that the evolution of the planet drives the evolution of the biosphere. There have been 2 significant stages in Earth history when atmospheric oxygen levels rose rapidly, and both appear to be associated with supercontinent cycles. The earlier biospheric event, which extends across the Archean-Proterozoic boundary (ca. 3.0-2.2 Ga), has received little attention and is the focus of this study. Recent work on the Pilbara Craton of Western Australia has shown that concretion formed by microbial activity during the diagenesis of these sediments are absent from early Archean sediments but abundant in late Archean and early Paleoproterozoic successions of the Hamersley Basin, appearing abruptly in sedimentary rocks younger than 2.7 Ga. This study suggests that their internal architecture may have been defined by the diffusion of humic acids and the formation of polymer gels during diagenesis. The data imply that the biosphere expanded suddenly shortly after 3.0 Ga and may have begun to raise the oxygen levels of the oceanic water column earlier than thought-possibly as much as 300 my earlier.     

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.     

Carbonaceous cherts in the Barberton greenstone belt and their significance for the study of early life in the Archean record

The 3.5-3.2 Ga old volcano-sedimentary succession of the Barberton greenstone belt (South Africa) is characterized by lithological units that are repeated in a regular manner. Komatiitic, basaltic, and dacitic volcanic and volcaniclastic sequences are capped by zones of silica enrichment, followed by bedded carbonaceous cherts. Stratiform and crosscutting carbonaceous chert veins are common in silica alteration zones and bedded cherts. A detailed field study of several chert horizons and chert veins that range in age from 3.47 to 3.30 Ga revealed the importance of syndepositional hydrothermal activity for their origin. Bedded cherts consist of silicified detrital and tuffaceous sediments that were deposited on the seafloor. Silicification took place at the sediment-water interface as a result of diffuse upflow of low-temperature hydrothermal fluids, which gave rise to the formation of impermeable chert caps. Fluid overpressure resulted in the breaching of the cap rocks at times. Chert veins contain angular host rock fragments, replace wall rocks, and show evidence of multiple vein fillings and in situ brecciation of earlier generations of vein fillings. They represent hydraulic fractures that were initiated by overpressuring of the hydrothermal system. The vein networks were infilled, partly by hydrothermal chert precipitates, and partly by still unconsolidated (not yet silicified) sedimentary material derived from overlying sedimentary horizons. Field, petrographic, isotopic, and trace element evidence indicate that most carbonaceous matter represents sedimentary material that originated by biogenic processes in the Archean oceans and not by hydrothermal processes in the subsurface.     

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.     

Clathrate hydrates of oxidants in the ice shell of Europa

Europa's icy surface is radiolytically modified by high-energy electrons and ions, and photolytically modified by solar ultraviolet photons. Observations from the Galileo Near Infrared Mapping Spectrometer, ground-based telescopes, the International Ultraviolet Explorer, and the Hubble Space Telescope, along with laboratory experiment results, indicate that the production of oxidants, such as H2O2, O2, CO2, and SO2, is a consequence of the surface radiolytic chemistry. Once created, some of the products may be entrained deeper into the ice shell through impact gardening or other resurfacing processes. The temperature and pressure environments of regions within the europan hydrosphere are expected to permit the formation of mixed clathrate compounds. The formation of carbon dioxide and sulfur dioxide clathrates has been examined in some detail. Here we add to this analysis by considering oxidants produced radiolytically on the surface of Europa. Our results indicate that the bulk ice shell could have a approximately 1.7-7.6% by number contamination of oxidants resulting from radiolysis at the surface. Oxidant-hosting clathrates would consequently make up approximately 12-53% of the ice shell by number relative to ice, if oxidants were entrained throughout. We examine, in brief, the consequences of such contamination on bulk ice shell thickness and find that clathrate formation could lead to substantially thinner ice shells on Europa than otherwise expected. Finally, we propose that double occupancy of clathrate cages by O2 molecules could serve as an explanation for the observation of condensed-phase O2 on Europa. Clathrate-sealed, gas-filled bubbles in the near surface ice could also provide an effective trapping mechanism, though they cannot explain the 5771 A (O2)2 absorption.     

Mineralization of wastes of human vital activity and plants to be used in a Life Support System

Available methods for mineralizing wastes of human activity and inedible biomass of plants used in this country and abroad are divided into two types: dry mineralization at high temperatures up to 1270 K with subsequent partial dissolution of the ash and the other--wet oxidation by acids. In this case mineralization is performed at a temperature of 470-460 K and a pressure of 220-270 atmospheres in pure oxygen with the output of mineral solution and dissoluble sediments in the form of scale. The drawback of the first method is the formation of dioxins, CO, SO2, NO2 and other toxic compounds. The latter method is too sophisticated and is presently confined to bench testing. The here proposed method to mineralize the wastes is in mid-position between the thermal and physical chemical methods. At a temperature of 80-90 degrees C the mixture was exposed to a controlled electromagnetic field at normal atmospheric pressure. The method merits simplicity, reliability, produces no dissoluble sediment or emissions noxious for human and plants. The basic difference from the above said methods is to employ as an oxidizer atomic oxygen, its active forms including OH-radicals with hydrogen peroxide as the source. Hydrogen peroxide can be produced with electric power from water inside the Life Support System (LSS).     

Availability of O(2) and H(2)O(2) on pre-photosynthetic Earth

Old arguments that free O(2) must have been available at Earth's surface prior to the origin of photosynthesis have been revived by a new study that shows that aerobic respiration can occur at dissolved oxygen concentrations much lower than had previously been thought, perhaps as low as 0.05?nM, which corresponds to a partial pressure for O(2) of about 4?×?10(-8) bar. We used numerical models to study whether such O(2) concentrations might have been provided by atmospheric photochemistry. Results show that disproportionation of H(2)O(2) near the surface might have yielded enough O(2) to satisfy this constraint. Alternatively, poleward transport of O(2) from the equatorial stratosphere into the polar night region, followed by downward transport in the polar vortex, may have brought O(2) directly to the surface. Thus, our calculations indicate that this "early respiration" hypothesis might be physically reasonable.     

TD-1HNMR measurements show enantioselective dissociation of ribose and glucose in the presence of H2(17)O

We used Time Domain (1)H Nuclear Magnetic Resonance (NMR) to characterize changes in proton exchange between water and sugar enantiomers at different concentrations of H(2)(17)O (approximately 15-450 mM) and found that dissociation of the (-)-enantiomers of glucose and ribose occurs at significantly higher rates at higher concentrations of H(2)(17)O. The mechanism behind this enantioselective effect is unclear. The hypothesis we propose is that the large magnetic field (B(o) approximately 0.6T) applied during NMR measurements induces electric moments opposite in sign for the D and L-isomers. Because (17)O has a nuclear electric quadrupole moment not = 0, asymmetrically hydrated complexes may form between the B(o)-polarized enantiomers and H(2)(17)O. Either H(2)(17)O is more often hydrating the (+) than the (-)-enantiomers--and consequently pK differences between H(2)(16)O and H(2)(17)O lead to differences in proton exchange between enantiomers and water--or the orientation of H(2)(17)O relative to the B(o)-polarized enantiomers is different, in total or in part, which leads to hydrated complexes with different spatial geometries and different proton exchange properties. This effect is significant for Magneto-Chiral Stereo-Chemistry (MCSC) and astrobiology, and it may help us better understand specific instances of mass independent isotopic fractionation and aid in the development of new technologies for chiral and isotopic separation.     

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.     

variations of the atmospheric chemical composition in the earths’s polar regions after solar proton flare on July 14, 2000 (photochemical simulation)

Altitude—temporal cross-sections q(z, t) of atmospheric ionization rates by solar protons above the polar regions were calculated using the GOES-10 satellite data on solar proton fluxes for the period of solar proton flare (SPF) on July 14, 2000. The values of q(z, t) were used further in calculations of variations of the atmospheric chemical composition during the flare in the northern and southern polar regions (70°N and 70°S) by two different 1D photochemical models of the atmosphere (neutral and charged components). The calculation results have shown considerable variation of the ozone content after SPF: a decrease of [O3] was about 80% at altitudes of 65–75 km above northern and 25% in the layer of 55–65 km above the southern polar region. Such decrease of the ozone content is a result of reactions with [NO] and [OH] whose concentrations have grown substantially during SPF. According to calculations, the increase of electron concentration during SPF has reached 3–4 orders of magnitude at altitudes of 50–80 km. A comparison of the calculation results with the observational data on [NO], [NO2], and [O3] from the UARS and HALOE satellites for 70°N have shown a good qualitative correspondence, however, for variations of nitric oxides there are quantitative discrepancies.     

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.     

Substrate limitation for methanogenesis in hypersaline environments

Motivated by the increasingly abundant evidence for hypersaline environments on Mars and reports of methane in its atmosphere, we examined methanogenesis in hypersaline ponds in Baja California Sur, Mexico, and in northern California, USA. Methane-rich bubbles trapped within or below gypsum/halite crusts have δ13C values near -40‰. Methane with these relatively high isotopic values would typically be considered thermogenic; however, incubations of crust samples resulted in the biological production of methane with similar isotopic composition. A series of measurements aimed at understanding the isotopic composition of methane in hypersaline systems was therefore undertaken. Methane production rates, as well as the concentrations and isotopic composition of the particulate organic carbon (POC), were measured. Methane production was highest from microbial communities living within gypsum crusts, whereas POC content at gypsum/halite sites was low, generally less than 1% of the total mass. The isotopic composition of the POC ranged from -26‰ to -10‰. To determine the substrates used by the methanogens, 13C-labeled methylamines, methanol, acetate, and bicarbonate were added to individual incubation vials, and the methane produced was monitored for 13C content. The main substrates used by the methanogens were the noncompetitive substrates, the methylamines, and methanol. When unlabeled trimethylamine (TMA) was added to incubating gypsum/halite crusts in increasing concentrations, the isotopic composition of the methane produced became progressively lower; the lowest methane δ13C values occurred when the most TMA was added (1000 μM final concentration). This decrease in the isotopic composition of the methane produced with increasing TMA concentrations, along with the high in situ methane δ13C values, suggests that the methanogens within the crusts are operating at low substrate concentrations. It appears that substrate limitation is decreasing isotopic fractionation during methanogenesis, which results in these abnormally high biogenic methane δ13C values.     

Acetylene as fast food: implications for development of life on anoxic primordial Earth and in the outer solar system

Acetylene occurs, by photolysis of methane, in the atmospheres of jovian planets and Titan. In contrast, acetylene is only a trace component of Earth's current atmosphere. Nonetheless, a methane-rich atmosphere has been hypothesized for early Earth; this atmosphere would also have been rich in acetylene. This poses a paradox, because acetylene is a potent inhibitor of many key anaerobic microbial processes, including methanogenesis, anaerobic methane oxidation, nitrogen fixation, and hydrogen oxidation. Fermentation of acetylene was discovered approximately 25 years ago, and Pelobacter acetylenicus was shown to grow on acetylene by virtue of acetylene hydratase, which results in the formation of acetaldehyde. Acetaldehyde subsequently dismutates to ethanol and acetate (plus some hydrogen). However, acetylene hydratase is specific for acetylene and does not react with any analogous compounds. We hypothesize that microbes with acetylene hydratase played a key role in the evolution of Earth's early biosphere by exploiting an available source of carbon from the atmosphere and in so doing formed protective niches that allowed for other microbial processes to flourish. Furthermore, the presence of acetylene in the atmosphere of a planet or planetoid could possibly represent evidence for an extraterrestrial anaerobic ecosystem.     

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.