Hydrogen emission in meteors as a potential marker for the exogenous delivery of organics and water

We detected hydrogen Balmer-alpha (H(alpha)) emission in the spectra of bright meteors and investigated its potential use as a tracer for exogenous delivery of organic matter. We found that it is critical to observe the meteors with high enough spatial resolution to distinguish the 656.46 nm H(alpha) emission from the 657.46 nm intercombination line of neutral calcium, which was bright in the meteor afterglow. The H(alpha) line peak stayed in constant ratio to the atmospheric emissions of nitrogen during descent of the meteoroid. If all of the hydrogen originates in the Earth's atmosphere, the hydrogen atoms are expected to have been excited at T = 4400 K. In that case, we measured an H(2)O abundance in excess of 150 +/- 20 ppm at 80-90 km altitude (assuming local thermodynamic equilibrium in the air plasma). This compares with an expected <20 ppm from H(2)O in the gas phase. Alternatively, meteoric refractory organic matter (and water bound in meteoroid minerals) could have caused the observed H(alpha) emission, but only if the line is excited in a hot T approximately 10000 K plasma component that is unique to meteoric ablation vapor emissions such as Si(+). Assuming that the Si(+) lines of the Leonid spectrum would need the same hot excitation conditions, and a typical [H]/[C] = 1 in cometary refractory organics, we calculated an abundance ratio [C]/[Si] = 3.9 +/- 1.4 for the dust of comet 55P/Tempel-Tuttle. This range agreed with the value of [C]/[Si] = 4.4 measured for comet 1P/Halley dust. Unless there is 10 times more water vapor in the upper atmosphere than expected, we conclude that a significant fraction of the hydrogen atoms in the observed meteor plasma originated in the meteoroid.     

Search for the OH (X(2)Pi) Meinel band emission in meteors as a tracer of mineral water in comets: detection of N(2)(+) (A-X)

We report the discovery of the N(2)(+) A-X Meinel band in the 780-840 nm meteor emission from two Leonid meteoroids that were ejected less than 1000 years ago by comet 55P/Tempel-Tuttle. Our analysis indicates that the N(2)(+) molecule is at least an order of magnitude less abundant than expected, possibly as a result of charge transfer reactions with meteoric metal atoms. This new band was found while searching for rovibrational transitions in the X(2)Pi electronic ground state of OH (the OH Meinel band), a potential tracer of water bound to minerals in cometary matter. The electronic A-X transition of OH has been identified in other Leonid meteors. We did not detect this OH Meinel band, which implies that the excited A state is not populated by thermal excitation but by a mechanism that directly produces OH in low vibrational levels of the excited A(2)Sigma state. Ultraviolet dissociation of atmospheric or meteoric water vapor is such a mechanism, as is the possible combustion of meteoric organics.     

The mass and speed dependence of meteor air plasma temperatures

The speed and mass dependence of meteor air plasma temperatures is perhaps the most important data needed to understand how small meteoroids chemically change the ambient atmosphere in their path and enrich the ablated meteoric organic matter with oxygen. Such chemistry can play an important role in creating prebiotic compounds. The excitation conditions in various air plasma emissions were measured from high-resolution optical spectra of Leonid storm meteors during NASA's Leonid Multi-Instrument Aircraft Campaign. This was the first time a sufficient number and range of temperature measurements were obtained to search for meteoroid mass and speed dependencies. We found slight increases in temperature with decreasing altitude, but otherwise nearly constant values for meteoroids with speeds between 35 and 72 km/s and masses between 10(-5) g and 1 g. We conclude that faster and more massive meteoroids produce a larger emission volume, but not a higher air plasma temperature. We speculate that the meteoric plasma may be in multiphase equilibrium with the ambient atmosphere, which could mean lower plasma temperatures in a CO(2)-rich early Earth atmosphere.     

Meteor wake in high frame-rate images--implications for the chemistry of ablated organic compounds

Extraterrestrial organic matter may have been chemically altered into forms more ameanable for prebiotic chemistry in the wake of a meteor after ablation. We measured the rate of cooling of the plasma in the meteor wake from the intensity decay just behind a meteoroid by freezing its motion in high frame-rate 1000 frames/s video images, with an intensified camera that has a short phosphor decay time. Though the resulting cooling rate was found to be lower than theoretically predicted, our calculations indicated that there would have been insufficient collisions to break apart large organic compounds before most reactive radicals and electrons were lost from the air plasma. Organic molecules delivered from space to the early Earth via meteors might therefore have survived in a chemically altered form. In addition, we discovered that relatively small meteoroids generated far-ultraviolet emission that is absorbed in the immediate environment of the meteoroid, which may chemically alter the atmosphere over a much larger region than previously recognized.     

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.     

Results of impact simulation for the GIOTTO mission

The European Space Agency (ESA) has decided to carry out a fly-by mission to the comet Halley. The spacecraft will be launched by an ARIANE II and intercept the retrograde Halley orbit on 13 March, 1986. One group of experiments is designed to obtain data on size, mass and composition of the dust in the cometary tail. Because of the very high relative velocity during fly-by (69 km/s) laboratory experiments are necessary to develop and calibrate the experiments. These experiments are presently under way in the laboratory of the Lehrstuhl für Raumfahrttechnik of the Technische Universität München. First results have been obtained for both the Dust Impact Detection System (DIDSY) and the P?articulate Impact Analyzer (PIA). These results are compared with the theoretical models for hypervelocity impact craters. The agreement is good at impact velocities around 15 km/s.     

A transmission electron microscopy study of silica and kerogen biosignatures in approximately 1.9 Ga gunflint microfossils

Microfossils preserved in chert from the;1.9 Ga Gunflint Formation (Schreiber Beach, Ontario, Canada) were studied with transmission electron microscopy (TEM) and analytical TEM (ATEM). Our goals were to uncover the style of silicification relative to the distribution of organic matter, and to evaluate the distribution and evolution of organic matter, at submicroscopic spatial scales. Petrographically the microfossils typically display filamentous or coccoidal morphologies, and consist of quartz crystals surrounded by kerogen along grain boundaries. ATEM analysis revealed that quartz associated with kerogen consists of 200-500nm-sized, round crystallites, whereas the chert matrix is comprised of randomly oriented, polygonal microquartz (5-10 microm). Silica spheroids found within some fossils consist of quartz subgrains in an amorphous to poorly crystalline matrix, suggesting that precipitation of opaline silica on organic matter occurred with subsequent but incomplete transformation to quartz. Some coccoidal microfossils surround large euhedral quartz crystals (up to 5 microm in diameter) that appeared to have influenced the distribution of kerogen during crystal growth. These euhedral quartz crystals commonly contain elongated (50-100 nm) iron-rich crystallites. Energy-loss, near-edge structure analysis of kerogen associated with a coccoidal microfossil showed that it is composed of amorphous carbon with no evidence of graphitization. TEM results revealed significant differences in the style of silicification between microbe-shaped microfossils and their surrounding chert matrix, as well as the presence of amorphous kerogen.     

Exploitation of new materials processing in a mega-gravity field

A strong acceleration field (mega-gravity) can cause the sedimentation of even atoms and is expected to create an unique one-dimensional crystal strain state, i.e. an instability in molecular or crystalline state in multi-component condensed matter. However, materials science research under the mega-gravity field has now remained unexploited, while microgravity has been much used in many fields. We developed a self-consistent theory for sedimentation of atoms in condensed matter, and an ultracentrifuge apparatus to generate an acceleration of over 1 million (1×10⁶)g at high temperature. Recently, we for the first time formed an atomic-scale-graded structure by the sedimentation of atoms, and observed crystal growth in an alloy under a mega-gravity field. It is expected that the availability of mega-gravity may offer us new and powerful options in materials processing in terms of controlling compositions even of isotopes, of forming atomic-scale-graded structure or nonstoichiometric structure, and of controlling the ordering of atoms or molecules.     

Ballistics of a fragmenting meteor body with allowance made for ablation in the non-isothermal atmosphere. II

The second part of the work is devoted to studying the motion of fragmenting meteor bodies with ablation by fragments in a planet’s atmosphere, taking into account its non-isothermal character in altitude. The mechanical fragmentation of a meteoroid under the action of aerodynamic drag is considered in the context of statistical strength theory. An analytical solution for ballistics of a fragmenting body is obtained at a constant parameter of ablation. A theoretical analysis of the derived regularities is made and an example of their usage in the problem of a comet-asteroid hazard is presented.     

The PROCESS experiment: amino and carboxylic acids under Mars-like surface UV radiation conditions in low-earth orbit

The search for organic molecules at the surface of Mars is a top priority of the next Mars exploration space missions: Mars Science Laboratory (NASA) and ExoMars (ESA). The detection of organic matter could provide information about the presence of a prebiotic chemistry or even biological activity on this planet. Therefore, a key step in interpretation of future data collected by these missions is to understand the preservation of organic matter in the martian environment. Several laboratory experiments have been devoted to quantifying and qualifying the evolution of organic molecules under simulated environmental conditions of Mars. However, these laboratory simulations are limited, and one major constraint is the reproduction of the UV spectrum that reaches the surface of Mars. As part of the PROCESS experiment of the European EXPOSE-E mission on board the International Space Station, a study was performed on the photodegradation of organics under filtered extraterrestrial solar electromagnetic radiation that mimics Mars-like surface UV radiation conditions. Glycine, serine, phthalic acid, phthalic acid in the presence of a mineral phase, and mellitic acid were exposed to these conditions for 1.5 years, and their evolution was determined by Fourier transform infrared spectroscopy after their retrieval. The results were compared with data from laboratory experiments. A 1.5-year exposure to Mars-like surface UV radiation conditions in space resulted in complete degradation of the organic compounds. Half-lives between 50 and 150?h for martian surface conditions were calculated from both laboratory and low-Earth orbit experiments. The results highlight that none of those organics are stable under low-Earth orbit solar UV radiation conditions.     

Spectral signatures of photosynthesis. II. Coevolution with other stars and the atmosphere on extrasolar worlds

As photosynthesis on Earth produces the primary signatures of life that can be detected astronomically at the global scale, a strong focus of the search for extrasolar life will be photosynthesis, particularly photosynthesis that has evolved with a different parent star. We take previously simulated planetary atmospheric compositions for Earth-like planets around observed F2V and K2V, modeled M1V and M5V stars, and around the active M4.5V star AD Leo; our scenarios use Earth's atmospheric composition as well as very low O2 content in case anoxygenic photosynthesis dominates. With a line-by-line radiative transfer model, we calculate the incident spectral photon flux densities at the surface of the planet and under water. We identify bands of available photosynthetically relevant radiation and find that photosynthetic pigments on planets around F2V stars may peak in absorbance in the blue, K2V in the red-orange, and M stars in the near-infrared, in bands at 0.93-1.1 microm, 1.1-1.4 microm, 1.5-1.8 microm, and 1.8-2.5 microm. However, underwater organisms will be restricted to wavelengths shorter than 1.4 microm and more likely below 1.1 microm. M star planets without oxygenic photosynthesis will have photon fluxes above 1.6 microm curtailed by methane. Longer-wavelength, multi-photo-system series would reduce the quantum yield but could allow for oxygenic photosystems at longer wavelengths. A wavelength of 1.1 microm is a possible upper cutoff for electronic transitions versus only vibrational energy; however, this cutoff is not strict, since such energetics depend on molecular configuration. M star planets could be a half to a tenth as productive as Earth in the visible, but exceed Earth if useful photons extend to 1.1 microm for anoxygenic photosynthesis. Under water, organisms would still be able to survive ultraviolet flares from young M stars and acquire adequate light for growth.     

Chaotic exchange of solid material between planetary systems: implications for lithopanspermia

Abstract We examined a low-energy mechanism for the transfer of meteoroids between two planetary systems embedded in a star cluster using quasi-parabolic orbits of minimal energy. Using Monte Carlo simulations, we found that the exchange of meteoroids could have been significantly more efficient than previously estimated. Our study is relevant to astrobiology, as it addresses whether life on Earth could have been transferred to other planetary systems in the Solar System's birth cluster and whether life on Earth could have been transferred from beyond the Solar System. In the Solar System, the timescale over which solid material was delivered to the region from where it could be transferred via this mechanism likely extended to several hundred million years (as indicated by the 3.8-4.0?Ga epoch of the Late Heavy Bombardment). This timescale could have overlapped with the lifetime of the Solar birth cluster (～100-500?Myr). Therefore, we conclude that lithopanspermia is an open possibility if life had an early start. Adopting parameters from the minimum mass solar nebula, considering a range of planetesimal size distributions derived from observations of asteroids and Kuiper Belt objects and theoretical coagulation models, and taking into account Oort Cloud formation models, we discerned that the expected number of bodies with mass>10?kg that could have been transferred between the Sun and its nearest cluster neighbor could be of the order of 10(14) to 3·10(16), with transfer timescales of tens of millions of years. We estimate that of the order of 3·10(8)·l (km) could potentially be life-bearing, where l is the depth of Earth's crust in kilometers that was ejected as the result of the early bombardment. Key Words: Extrasolar planets-Interplanetary dust-Interstellar meteorites-Lithopanspermia. Astrobiology 12, 754-774.     

Detectability of planetary characteristics in disk-averaged spectra II: synthetic spectra and light-curves of earth

Spatially and spectrally resolved models were used to explore the observational sensitivity to changes in atmospheric and surface properties and the detectability of surface biosignatures in the globally averaged spectra and light-curves of the Earth. Compared with previous efforts to characterize the Earth using disk-averaged models, a more comprehensive and realistic treatment of the surface and atmosphere was taken into account here. Our results are presented as a function of viewing geometry and phases at both visible/near-infrared (0.5-1.7 microm) and mid-infrared (5-25 microm) wavelength ranges, applicable to the proposed NASA-Terrestrial Planet Finder visible coronagraph and mid-infrared interferometer and to the ESADarwin mission architectures. Clouds can change the thermal emission by as much as 50% compared with the cloud-free case and increase the visible albedo by up to 500% for completely overcast cases at the dichotomy phase. Depending on the observed phase and their distribution and type, clouds can also significantly alter the spectral shape. Moreover, clouds impact the detectability of surface biosignatures in the visible wavelength range. Modeling the disk-averaged sensitivity to the "red-edge," a distinctive spectral signature of vegetation, showed that Earth's land vegetation could be seen in disk-averaged spectra, even with cloud cover, when the signal was averaged over the daily time scale. We found that vegetation is more readily discriminated from clouds at dichotomy (50% illumination) rather than at full phase. The detectability of phytoplankton was also explored, but was found to be more difficult to detect in the disk-average than land vegetation.     

Searching for life on Mars: selection of molecular targets for ESA's aurora ExoMars mission

The European Space Agency's ExoMars mission will seek evidence of organic compounds of biological and non-biological origin at the martian surface. One of the instruments in the Pasteur payload may be a Life Marker Chip that utilizes an immunoassay approach to detect specific organic molecules or classes of molecules. Therefore, it is necessary to define and prioritize specific molecular targets for antibody development. Target compounds have been selected to represent meteoritic input, fossil organic matter, extant (living, recently dead) organic matter, and contamination. Once organic molecules are detected on Mars, further information is likely to derive from the detailed distribution of compounds rather than from single molecular identification. This will include concentration gradients beneath the surface and gradients from generic to specific compounds. The choice of biomarkers is informed by terrestrial biology but is wide ranging, and nonterrestrial biology may be evident from unexpected molecular distributions. One of the most important requirements is to sample where irradiation and oxidation are minimized, either by drilling or by using naturally excavated exposures. Analyzing regolith samples will allow for the search of both extant and fossil biomarkers, but sequential extraction would be required to optimize the analysis of each of these in turn.     

环三磷腈基多官能液体环氧树脂(HGCP)的合成与热性能

以六氯环三磷腈、2,3-环氧基-1-丙醇为原料,得到六缩水甘油基环三磷腈(HGCP)。通过红外、核磁、质谱及元素分析对产物结构进行了表征,并研究了溶剂、原料配比、反应温度和时间对反应的影响。结果表明,合成的最佳条件是:四氢呋喃为溶剂,反应物料配比为n(2,3-环氧基-1-丙醇):n(六氯环三磷腈)=7.62,反应温度为30℃,反应时间4.0 h,产品收率达到78%。选取顺丁烯二酸酐(MA)和4,4-二氨基-二苯-甲烷(MDA)为固化剂,通过热失重分析和线烧蚀率研究了不同固化体系的耐热性和耐烧蚀性。研究表明,六缩水甘油基环三磷腈表现出优良的热稳定性,其交联产物EPG-1和EPG-2在高温条件下残炭量较高,线烧蚀率分别为0.344 mm/s和0.364 mm/s,可作为固体火箭推进剂绝热包覆材料使用。     

Biomarker and stable isotope characterization of coastal pond-derived organic matter, McMurdo Dry Valleys, Antarctica

Small coastal ponds that contain photosynthetic microbial mat communities represent an extreme environment where a potentially significant source of labile organic carbon can be found within the McMurdo Dry Valleys, Antarctica. To distinguish coastal pond-derived organic matter from other sources of organic matter in the Dry Valleys, bulk organic carbon, nitrogen, and sulfur isotope signatures and phospholipid fatty acid (PLFA) profiles of benthic microbial mats located at two sites--Hjorth Hill coast and Garwood Valley--were investigated. The average isotope values at Hjorth Hill coast and Garwood Valley are, respectively, -10.9 per thousand and -10.2 per thousand for delta(13) C, 3.7 per thousand and -1.3 per thousand for delta(15)N, and 8.1 per thousand and 16.7 per thousand for delta(34)S. Microbial mats from all ponds are dominated by monounsaturated PLFAs (indicative of Gram-negative bacteria) and polyunsaturated PLFAs (indicative of microeukaryotes). Biomarkers specific to aerobic prokaryotes, eukaryotes, and photoautotrophic microeukaryotes, as well as sulfur-reducing bacteria, are present in all samples. Benthic mats at Garwood Valley are thicker and more laminated, have a higher biomass, and have a greater carbon and nitrogen content, which suggests greater productivity than mats at Hjorth Hill coast. Greater productivity is supported, as well, by higher dissolved oxygen contents likely derived from heightened photosynthetic productivity. More productivity at Garwood Valley likely results from a larger influx of terrestrial surface waters together with a concomitant nutrient loading.     

Multifrequency electron spin resonance detection of solid-state organic free radicals in HCN polymer and a Titan tholin

Macromolecules derived from hydrogen cyanide (HCN) may be major components of the dark matter observed in bodies in the outer Solar System, which include comets and asteroids. HCN oligomers and polymers are readily formed at room temperature and react with water to produce polypeptides and alpha-amino acids or undergo pyrolysis to produce nitrogen heterocycles. Electron spin resonance (ESR) spectroscopy shows that HCN polymer mixtures contain a significant amount of long-lived organic free radicals that are primarily carbon-based. For comparison, we have also examined samples of tholins produced from experimental analogs of Titan aerosols, which has been shown by trace organic analysis to consist partly of HCN polymer. The "Titan tholin" exhibits at least two ESR signals that can be assigned to nitrogen- and carbon-centered radicals, although heating the sample eliminates the nitrogen centers and increases the signal from the carbon centers. This result suggests that the nitrogen-centered radicals may be thermodynamically less stable, but are kinetically trapped during the spark-discharge reactions that produce tholins from mixtures of gases such as methane and nitrogen. The results strongly support previous proposals of free radical mechanisms for HCN polymerization.     

Effects of HZE particle on the nigrostriatal dopaminergic system in a future Mars mission

Because of long duration travel outside the Earth's magnetic field, the effect of iron-rich high charge and energy (HZE) particles in Galactic Cosmic Rays on human body is the major concern in radiation protection. Recently attention has been directed to effects on the central nervous system in addition to mutagenic effects. In particular, a reduction in striatal dopamine content on nigrostriatal dopaminergic system has been reported by investigators using accelerated iron ions in ground-based mammalian studies. In addition, studies of the pathophysiology of Parkinson's disease demonstrated that excess iron cause a reduction in the dopamine content in the substantia nigra. This suggests an intriguing possibility to explain the selective detrimental effects of HZE particles on the dopaminergic system. Should these particles have biochemical effects, possible options for countermeasures are: (1) nutritional prevention, (2) medication, and (3) surgical placement of a stimulator electrode at a specific anatomic site in the basal ganglia.     

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.     

Aqueous corrosion of phosphide minerals from iron meteorites: a highly reactive source of prebiotic phosphorus on the surface of the early Earth

We present the results of an experimental study of aqueous corrosion of Fe-phosphide under conditions relevant to the early Earth. The results strongly suggest that iron meteorites were an important source of reactive phosphorus (P), a requirement for the formation of P-based life. We further demonstrate that iron meteorites were an abundant source of phosphide minerals early in Earth history. Phosphide corrosion was studied in five different solutions: deionized water, deionized water buffered with sodium bicarbonate, deionized water with dissolved magnesium and calcium chlorides, deionized water containing ethanol and acetic acid, and deionized water containing the chlorides, ethanol, and acetic acid. Experiments were performed in the presence of both air and pure Ar gas to evaluate the effect of atmospheric chemistry. Phosphide corrosion in deionized water results in a metastable mixture of mixed-valence, P-bearing ions including pyrophosphate and triphosphate, key components for metabolism in modern life. In a pH-buffered solution of NaHCO(3), the condensed and reduced species diphosphonate is an abundant corrosion product. Corrosion in ethanol- and acetic acid-containing solutions yields additional P-bearing organic molecules, including acetyl phosphonate and a cyclic triphosphorus molecule. Phosphonate is a major corrosion product of all experiments and is the only P-bearing molecule that persists in solutions with high concentrations of magnesium and calcium chlorides, which suggests that phosphonate may have been a primitive oceanic source of P. The stability and reactivity of phosphonate and hypophosphite in solution were investigated to elucidate reaction mechanisms and the role of mineral catalysts on P-solution chemistry. Phosphonate oxidation is rapid in the presence of Fe metal but negligible in the presence of magnetite and in the control sample. The rate of hypophosphite oxidation is independent of reaction substrate.