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.     

Oxidant enhancement in martian dust devils and storms: storm electric fields and electron dissociative attachment

Laboratory studies, numerical simulations, and desert field tests indicate that aeolian dust transport can generate atmospheric electricity via contact electrification or "triboelectricity." In convective structures such as dust devils and dust storms, grain stratification leads to macroscopic charge separations and gives rise to an overall electric dipole moment in the aeolian feature, similar in nature to the dipolar electric field generated in terrestrial thunderstorms. Previous numerical simulations indicate that these storm electric fields on Mars can approach the ambient breakdown field strength of approximately 25 kV/m. In terrestrial dust phenomena, potentials ranging from approximately 20 to 160 kV/m have been directly measured. The large electrostatic fields predicted in martian dust devils and storms can energize electrons in the low pressure martian atmosphere to values exceeding the electron dissociative attachment energy of both CO2 and H2O, which results in the formation of the new chemical products CO/O- and OH/H-, respectively. Using a collisional plasma physics model, we present calculations of the CO/O- and OH/H- reaction and production rates. We demonstrate that these rates vary geometrically with the ambient electric field, with substantial production of dissociative products when fields approach the breakdown value of approximately 25 kV/m. The dissociation of H2O into OH/H- provides a key ingredient for the generation of oxidants; thus electrically charged dust may significantly impact the habitability of Mars.     

Recurrent isolation of hydrogen peroxide-resistant spores of Bacillus pumilus from a spacecraft assembly facility

While the microbial diversity of a spacecraft assembly facility at the Jet Propulsion Laboratory (Pasadena, CA) was being monitored, H2O2-resistant bacterial strains were repeatedly isolated from various surface locations. H2O2 is a possible sterilant for spacecraft hardware because it is a low-temperature process and compatible with various modern-day spacecraft materials, electronics, and components. Both conventional biochemical testing and molecular analyses identified these strains as Bacillus pumilus. This Bacillus species was found in both unclassified (entrance floors, anteroom, and air-lock) and classified (floors, cabinet tops, and air) locations. Both vegetative cells and spores of several B. pumilus isolates were exposed to 5% liquid H2O2 for 60 min. Spores of each strain exhibited higher resistance than their respective vegetative cells to liquid H2O2. Results indicate that the H2O2 resistance observed in both vegetative cells and spores is strain-specific, as certain B. pumilus strains were two to three times more resistant than a standard Bacillus subtilis dosimetry strain. An example of this trend was observed when the type strain of B. pumilus, ATCC 7061, proved sensitive, whereas several environmental strains exhibited varying degrees of resistance, to H2O2. Repeated isolation of H2O2-resistant strains of B. pumilus in a clean-room is a concern because their persistence might potentially compromise life-detection missions, which have very strict cleanliness and sterility requirements for spacecraft hardware.     

Oxidant enhancement in martian dust devils and storms: implications for life and habitability

We investigate a new mechanism for producing oxidants, especially hydrogen peroxide (H2O2), on Mars. Large-scale electrostatic fields generated by charged sand and dust in the martian dust devils and storms, as well as during normal saltation, can induce chemical changes near and above the surface of Mars. The most dramatic effect is found in the production of H2O2 whose atmospheric abundance in the "vapor" phase can exceed 200 times that produced by photochemistry alone. With large electric fields, H2O2 abundance gets large enough for condensation to occur, followed by precipitation out of the atmosphere. Large quantities of H2O2 would then be adsorbed into the regolith, either as solid H2O2 "dust" or as re-evaporated vapor if the solid does not survive as it diffuses from its production region close to the surface. We suggest that this H2O2, or another superoxide processed from it in the surface, may be responsible for scavenging organic material from Mars. The presence of H2O2 in the surface could also accelerate the loss of methane from the atmosphere, thus requiring a larger source for maintaining a steady-state abundance of methane on Mars. The surface oxidants, together with storm electric fields and the harmful ultraviolet radiation that readily passes through the thin martian atmosphere, are likely to render the surface of Mars inhospitable to life as we know it.     

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.     

90 keV电子辐照对Kapton H薄膜化学结构的影响

文章研究了能量为90 keV的电子辐照对Kapton H薄膜化学结构的影响。XPS分析表明,低能电子辐照导致Kapton H薄膜分子结构中C—N和C—O键的断裂,以及C＝O键的断裂和重组,并且有部分键断裂后交联。随着辐照剂量及辐照能量的增加,材料中的C—N、C＝O键含量减少,形成表面碳富集。辐照使柔性结构C—O键被破坏,产生的交联及以苯环为主的三维立体网状结构使其表面硬度增加。     

Fine structure of interplanetary shock fronts from the data of the BMSW instrument of the PLASMA-F experiment

The paper is concerned with studying the thickness of fronts of 38 interplanetary shocks detected by the BMSW instrument, which is a part of the scientific payload of the SPEKTR-R spacecraft, which was launched into a highly elliptical orbit in 2011. The main parameters of the interplanetary shocks have been calculated as follows: the ratio of thermal pressure to magnetic pressure before the front β, the angle between the shock front normal and the undisturbed magnetic field θ_Bn, the ratio of the shock propagation velocity to the magnetosonic velocity in the undisturbed region M_ms, and the shock front velocity relative to the Earth. It has been shown that the front thickness determined from the plasma parameters approximately matches the front thickness obtained from the magnetic field measurements and lies between 0.5 and 5 proton inertial lengths. In some events, the oscillations have been observed (upstream and downstream of the shock) in plasma parameters and in the magnetic field data. The length has been found to be between 0.5 and 6 proton inertial lengths for the preceding oscillations and between 0.5 and 10 proton inertial lengths for the following oscillations. The average value of the proton inertial length is 62 km.     

Pyrite-induced hydrogen peroxide formation as a driving force in the evolution of photosynthetic organisms on an early earth

The remarkable discovery of pyrite-induced hydrogen peroxide (H2O2) provides a key step in the evolution of oxygenic photosynthesis. Here we show that H2O2 can be generated rapidly via a reaction between pyrite and H2O in the absence of dissolved oxygen. The reaction proceeds in the dark, and H2O2 levels increase upon illumination with visible light. Since pyrite was stable in most photic environments prior to the rise of O2 levels, this finding represents an important mechanism for the formation of H2O2 on early Earth.     

多孔硅树脂/聚二甲基硅氧烷复合材料的制备及其孔结构表征

采用甲基苯基硅树脂为树脂基体,嵌段共聚物聚二甲基硅氧烷-聚氧乙烯(PDMS-PEO)为模板剂,合成甲基苯基硅树脂/聚二甲基硅氧烷(MPS/PDMS)复合材料,并采用透射电镜(TEM)、氢核磁(1H NMR)和氮气吸附脱附等对所制备材料的结构和性能进行表征。结果表明,所制备的MPS/PDMS复合材料具有有序的介孔结构,其BET比表面积、孔容和平均孔径分别为285 m2/g、0.21 cm3/g和24.2 nm。     

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.     

Remote sensing of planetary properties and biosignatures on extrasolar terrestrial planets

The major goals of NASA's Terrestrial Planet Finder (TPF) and the European Space Agency's Darwin missions are to detect terrestrial-sized extrasolar planets directly and to seek spectroscopic evidence of habitable conditions and life. Here we recommend wavelength ranges and spectral features for these missions. We assess known spectroscopic molecular band features of Earth, Venus, and Mars in the context of putative extrasolar analogs. The preferred wavelength ranges are 7-25 microns in the mid-IR and 0.5 to approximately 1.1 microns in the visible to near-IR. Detection of O2 or its photolytic product O3 merits highest priority. Liquid H2O is not a bioindicator, but it is considered essential to life. Substantial CO2 indicates an atmosphere and oxidation state typical of a terrestrial planet. Abundant CH4 might require a biological source, yet abundant CH4 also can arise from a crust and upper mantle more reduced than that of Earth. The range of characteristics of extrasolar rocky planets might far exceed that of the Solar System. Planetary size and mass are very important indicators of habitability and can be estimated in the mid-IR and potentially also in the visible to near-IR. Additional spectroscopic features merit study, for example, features created by other biosignature compounds in the atmosphere or on the surface and features due to Rayleigh scattering. In summary, we find that both the mid-IR and the visible to near-IR wavelength ranges offer valuable information regarding biosignatures and planetary properties; therefore both merit serious scientific consideration for TPF and Darwin.     

Oxygen and Hydrogen Peroxide in the Early Evolution of Life on Earth: In silico Comparative Analysis of Biochemical Pathways

Abstract In the Universe, oxygen is the third most widespread element, while on Earth it is the most abundant one. Moreover, oxygen is a major constituent of all biopolymers fundamental to living organisms. Besides O(2), reactive oxygen species (ROS), among them hydrogen peroxide (H(2)O(2)), are also important reactants in the present aerobic metabolism. According to a widely accepted hypothesis, aerobic metabolism and many other reactions/pathways involving O(2) appeared after the evolution of oxygenic photosynthesis. In this study, the hypothesis was formulated that the Last Universal Common Ancestor (LUCA) was at least able to tolerate O(2) and detoxify ROS in a primordial environment. A comparative analysis was carried out of a number of the O(2)-and H(2)O(2)-involving metabolic reactions that occur in strict anaerobes, facultative anaerobes, and aerobes. The results indicate that the most likely LUCA possessed O(2)-and H(2)O(2)-involving pathways, mainly reactions to remove ROS, and had, at least in part, the components of aerobic respiration. Based on this, the presence of a low, but significant, quantity of H(2)O(2) and O(2) should be taken into account in theoretical models of the early Archean atmosphere and oceans and the evolution of life. It is suggested that the early metabolism involving O(2)/H(2)O(2) was a key adaptation of LUCA to already existing weakly oxic zones in Earth's primordial environment. Key Words: Hydrogen peroxide-Oxygen-Origin of life-Photosynthesis-Superoxide dismutase-Superoxide reductase. Astrobiology 12, 775-784.     

Infrared spectra and radiation stability of H2O2 ices relevant to Europa

In this paper we present spectra of H2O2-containing ices in the near- and mid-infrared (IR) regions. Spectral changes on warming are shown, as is a comparison of near-IR bands of H2O and H2O2-containing ices. An estimate of the A-value (absolute intensity) for the largest near- IR feature of H2O2 is given. Radiation-decay half-lives are reported for 19 K and 80 K, and are related to the surface radiation doses on Europa. The radiation data show that H2O2 destruction is slower at 80 K than 19 K, and are consistent with the claim that icy material in the outermost micrometer of Europa's surface has been heavily processed by radiation.     

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.     

Why O2 is required by complex life on habitable planets and the concept of planetary "oxygenation time"

Life is constructed from a limited toolkit: the Periodic Table. The reduction of oxygen provides the largest free energy release per electron transfer, except for the reduction of fluorine and chlorine. However, the bonding of O2 ensures that it is sufficiently stable to accumulate in a planetary atmosphere, whereas the more weakly bonded halogen gases are far too reactive ever to achieve significant abundance. Consequently, an atmosphere rich in O2 provides the largest feasible energy source. This universal uniqueness suggests that abundant O2 is necessary for the high-energy demands of complex life anywhere, i.e., for actively mobile organisms of approximately 10(-1)-10(0) m size scale with specialized, differentiated anatomy comparable to advanced metazoans. On Earth, aerobic metabolism provides about an order of magnitude more energy for a given intake of food than anaerobic metabolism. As a result, anaerobes do not grow beyond the complexity of uniseriate filaments of cells because of prohibitively low growth efficiencies in a food chain. The biomass cumulative number density, n, at a particular mass, m, scales as n (> m) proportional to m(-1) for aquatic aerobes, and we show that for anaerobes the predicted scaling is n proportional to m (-1.5), close to a growth-limited threshold. Even with aerobic metabolism, the partial pressure of atmospheric O2 (P(O2)) must exceed approximately 10(3) Pa to allow organisms that rely on O2 diffusion to evolve to a size approximately 10(3) m x P(O2) in the range approximately 10(3)-10(4) Pa is needed to exceed the threshold of approximately 10(2) m size for complex life with circulatory physiology. In terrestrial life, O(2) also facilitates hundreds of metabolic pathways, including those that make specialized structural molecules found only in animals. The time scale to reach P(O(2)) approximately 10(4) Pa, or "oxygenation time," was long on the Earth (approximately 3.9 billion years), within almost a factor of 2 of the Sun's main sequence lifetime. Consequently, we argue that the oxygenation time is likely to be a key rate-limiting step in the evolution of complex life on other habitable planets. The oxygenation time could preclude complex life on Earth-like planets orbiting short-lived stars that end their main sequence lives before planetary oxygenation takes place. Conversely, Earth-like planets orbiting long-lived stars are potentially favorable habitats for complex life.     

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.     

Production of oxidants by ion irradiation of water/carbon dioxide frozen mixtures

We present new experimental results on the formation of oxidants, such as hydrogen peroxide, ozone, and carbonic acid, under ion irradiation of icy mixtures of water/carbon dioxide at different ratios and temperatures (16 and 80 K). Pure water ice layers and mixtures with carbon dioxide were irradiated by 200 keV He+ ions. We found that the CO(2)/H(2)O ratio progressively decreased to a value of about 0.1, the H(2)O(2) production increased with increasing CO(2) abundance at both 16 and 80 K, and the CO and H(2)CO(3) production increased with increasing CO(2) abundance at 16 K. At 80 K, the synthesis of CO was less efficient because of the high volatility of the molecule that partially sublimed from the target. The production of carbonic acid was connected with the production of CO(3). O(3) was detected only after ion irradiation of CO(2)-rich mixtures. The experimental results are discussed with regard to the relevance they may have in the production of an energy source for a europan or a martian biosphere.     

行星际空间质子引起介质深层充电的GEANT4模拟研究

高通量的空间质子是导致行星际航天器深层充电的主要原因,基于辐射诱导电导率模 型（RIC）和粒子输运模拟工具GEANT4对介质材料在质子辐照条件下的深层充电问题进行了 预估。利用GEANT4-RIC充电计算方法,首先计算出10MeV质子在Kapton和Teflon中的注量和 剂量沉积曲线,进而根据电流连续性方程、泊松方程和电荷俘获方程组成的辐射诱导电导率 模型（RIC）求解出介质内电荷和电场分布,与介质击穿电场阈值对比作为其是否发生放电 的依据。模拟结果证实了对10MeV质子,在质子注量为3×10 12 ／cm 2时Kapton会发 生放电,而Teflon则不会发生放电的一般性试验结论。验证了GEANT4-RIC方法用于行星际航 天器介质材料质子充放电评价的可行性,为此类问题的解决奠定了基础。
     

Detectability of planetary characteristics in disk-averaged spectra. I: The Earth model

Over the next 2 decades, NASA and ESA are planning a series of space-based observatories to detect and characterize extrasolar planets. This first generation of observatories will not be able to spatially resolve the terrestrial planets detected. Instead, these planets will be characterized by disk-averaged spectroscopy. To assess the detectability of planetary characteristics in disk-averaged spectra, we have developed a spatially and spectrally resolved model of the Earth. This model uses atmospheric and surface properties from existing observations and modeling studies as input, and generates spatially resolved high-resolution synthetic spectra using the Spectral Mapping Atmospheric Radiative Transfer model. Synthetic spectra were generated for a variety of conditions, including cloud coverage, illumination fraction, and viewing angle geometry, over a wavelength range extending from the ultraviolet to the farinfrared. Here we describe the model and validate it against disk-averaged visible to infrared observations of the Earth taken by the Mars Global Surveyor Thermal Emission Spectrometer, the ESA Mars Express Omega instrument, and ground-based observations of earthshine reflected from the unilluminated portion of the Moon. The comparison between the data and model indicates that several atmospheric species can be identified in disk-averaged Earth spectra, and potentially detected depending on the wavelength range and resolving power of the instrument. At visible wavelengths (0.4-0.9 microm) O3, H2O, O2, and oxygen dimer [(O2)2] are clearly apparent. In the mid-infrared (5-20 microm) CO2, O3, and H2O are present. CH4, N2O, CO2, O3, and H2O are visible in the near-infrared (1-5 microm). A comprehensive three-dimensional model of the Earth is needed to produce a good fit with the observations.     

Evaluation of the specific power of a high-voltage generator based on the use of energy resources of the earth’s radiation belts

The feasibility of constructing a high-voltage electric generator (HEG) transforming kinetic energy of particles of the radiation belts into electric power is considered. The maximum specific power of the generator is theoretically evaluated for a particular case of setting it inside the natural radiation belts of the Earth (ERB). It is demonstrated that from the viewpoint of weight parameters, the suggested design of HEG is quite competitive (at least in the region of domination of the ERB proton flux) with power sources of low-thrust spacecraft operating on conventional principles.