Biological potential of Martian hydrothermal systems

A source of energy to power metabolism may be a limiting factor in the abundance and spatial distribution of past or extant life on Mars. Although a global average of chemical energy available for microbial metabolism and biomass production on Mars has been estimated previously, issues of how the energy is distributed and which particular environments have the greatest potential to support life remain unresolved. We address these issues using geochemical models to evaluate the amounts of chemical energy available in one potential biological environment, Martian hydrothermal systems. In these models, host rock compositions are based upon the compositions of Martian meteorites, which are reacted at high temperature with one of three groundwater compositions. For each model, the values for Gibbs energy of reactions that are important for terrestrial chemosynthetic organisms and likely representative for putative Martian microbes are calculated. Our results indicate that substantial amounts of chemical energy may be available in these systems, depending most sensitively upon the composition of the host rock. From the standpoint of sources of metabolic energy, it is likely that suitable environments exist to support Martian life.     

Temporal changes in fluid chemistry and energy profiles in the vulcano island hydrothermal system

In June 2003, the geochemical composition of geothermal fluids was determined at 9 sites in the Vulcano hydrothermal system, including sediment seeps, geothermal wells, and submarine vents. Compositional data were combined with standard state reaction properties to determine the overall Gibbs free energy (DeltaG(r) ) for 120 potential lithotrophic and heterotrophic reactions. Lithotrophic reactions in the H-O-N-S-C-Fe system were considered, and exergonic reactions yielded up to 120 kJ per mole of electrons transferred. The potential for heterotrophy was characterized by energy yields from the complete oxidation of 6 carboxylic acids- formic, acetic, propanoic, lactic, pyruvic, and succinic-with the following redox pairs: O(2)/H(2)O, SO(4) (2)/H(2)S, NO(3) ()/NH(4) (+), S(0)/H(2)S, and Fe(3)O(4)/Fe(2+). Heterotrophic reactions yielded 6-111 kJ/mol e(). Energy yields from both lithotrophic and heterotrophic reactions were highly dependent on the terminal electron acceptor (TEA); reactions with O(2) yielded the most energy, followed by those with NO(3) (), Fe(III), SO(4) (2), and S(0). When only reactions with complete TEA reduction were included, the exergonic lithotrophic reactions followed a similar electron tower. Spatial variability in DeltaG(r) was significant for iron redox reactions, owing largely to the wide range in Fe(2+) and H(+) concentrations. Energy yields were compared to those obtained for samples collected in June 2001. The temporal variations in geochemical composition and energy yields observed in the Vulcano hydrothermal system between 2001 and 2003 were moderate. The largest differences in DeltaG(r) over the 2 years were from iron redox reactions, due to temporal changes in the Fe(2+) and H(+) concentrations. The observed variations in fluid composition across the Vulcano hydrothermal system have the potential to influence not only microbial diversity but also the metabolic strategies of the resident microbial communities.     

The potential for lithoautotrophic life on Mars: application to shallow interfacial water environments

We developed a numerical model to assess the lithoautotrophic habitability of Mars based on metabolic energy, nutrients, water availability, and temperature. Available metabolic energy and nutrient sources were based on a laboratory-produced Mars-analog inorganic chemistry. For this specific reference chemistry, the most efficient lithoautotrophic microorganisms would use Fe(2+) as a primary metabolic electron donor and NO(3)(-) or gaseous O(2) as a terminal electron acceptor. In a closed model system, biomass production was limited by the electron donor Fe(2+) and metabolically required P, and typically amounted to approximately 800 pg of dry biomass/ml ( approximately 8,500 cells/ml). Continued growth requires propagation of microbes to new fecund environments, delivery of fresh pore fluid, or continued reaction with the host material. Within the shallow cryosphere--where oxygen can be accessed by microbes and microbes can be accessed by exploration-lithoautotrophs can function within as little as three monolayers of interfacial water formed either by adsorption from the atmosphere or in regions of ice stability where temperatures are within some tens of degrees of the ice melting point. For the selected reference host material (shergottite analog) and associated inorganic fluid chemistry, complete local reaction of the host material potentially yields a time-integrated biomass of approximately 0.1 mg of dry biomass/g of host material ( approximately 10(9) cells/g). Biomass could also be sustained where solutes can be delivered by advection (cryosuction) or diffusion in interfacial water; however, both of these processes are relatively inefficient. Lithoautotrophs in near-surface thin films of water, therefore, would optimize their metabolism by deriving energy and nutrients locally. Although the selected chemistry and associated model output indicate that lithoautotrophic microbial biomass could accrue within shallow interfacial water on Mars, it is likely that these organisms would spend long periods in maintenance or survival modes, with instantaneous biomass comparable to or less than that observed in extreme environments on Earth.     

Genesis and preservation of a uranium-rich paleozoic epithermal system with a surface expression (Northern Flinders Ranges, South Australia): radiogenic heat driving regional hydrothermal circulation over geological timescales

The surface expressions of hydrothermal systems are prime targets for astrobiological exploration, and fossil systems on Earth provide an analogue to guide this endeavor. The Paleozoic Mt. Gee-Mt. Painter system (MGPS) in the Northern Flinders Ranges of South Australia is exceptionally well preserved and displays both a subsurface quartz sinter (boiling horizon) and remnants of aerial sinter pools that lie in near-original position. The energy source for the MGPS is not related to volcanism but to radiogenic heat produced by U-Th-K-rich host rocks. This radiogenic heat source drove hydrothermal circulation over a long period of time (hundreds of millions of years, from Permian to present), with peaks in hydrothermal activity during periods of uplift and high water supply. This process is reflected by ongoing hot spring activity along a nearby fault. The exceptional preservation of the MGPS resulted from the lack of proximal volcanism, coupled with tectonics driven by an oscillating far-field stress that resulted in episodic basement uplift. Hydrothermal activity caused the remobilization of U and rare earth elements (REE) in host rocks into (sub)economic concentrations. Radiogenic-heat-driven systems are attractive analogues for environments that can sustain life over geological times; the MGPS preserves evidence of episodic fluid flow for the past ～300 million years. During periods of reduced hydrothermal activity (e.g., limited water supply, quiet tectonics), radiolytic H(2) production has the potential to support an ecosystem indefinitely. Remote exploration for deposits similar to those at the MGPS systems can be achieved by combining hyperspectral and gamma-ray spectroscopy.     

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.     

Lithopanspermia in star-forming clusters

This paper considers the lithopanspermia hypothesis in star-forming groups and clusters, where the chances of biological material spreading from one solar system to another is greatly enhanced (relative to action in the field) because of the close proximity of the systems and lower relative velocities. These effects more than compensate for the reduced time spent in such crowded environments. This paper uses approximately 300,000 Monte Carlo scattering calculations to determine the cross sections for rocks to be captured by binaries and provides fitting formulae for other applications. We assess the odds of transfer as a function of the ejection speed v (eject) and number N(.) of members in the birth aggregate. The odds of any given ejected meteoroid being recaptured by another solar system are relatively low, about 1:10(3)-10(6) over the expected range of ejection speeds and cluster sizes. Because the number of ejected rocks (with mass m > 10 kg) per system can be large, N (R) approximately 10(16), virtually all solar systems are likely to share rocky ejecta with all of the other solar systems in their birth cluster. The number of ejected rocks that carry living microorganisms is much smaller and less certain, but we estimate that N (B) approximately 10(7) rocks can be ejected from a biologically active solar system. For typical birth environments, the capture of life-bearing rocks is expected to occur N (bio) asymptotically equal to 10-16,000 times (per cluster), depending on the ejection speeds. Only a small fraction (f (imp) approximately 10(4)) of the captured rocks impact the surfaces of terrestrial planets, so that N (lps) asymptotically equal to 10(3)-1.6 lithopanspermia events are expected per cluster (under favorable conditions). Finally, we discuss the question of internal versus external seeding of clusters and the possibility of Earth seeding young clusters over its biologically active lifetime.     

Serpentinization and its implications for life on the early Earth and Mars

Ophiolites, sections of ocean crust tectonically displaced onto land, offer significant potential to support chemolithoautotrophic life through the provision of energy and reducing power during aqueous alteration of their highly reduced mineralogies. There is substantial chemical disequilibrium between the primary olivine and pyroxene mineralogy of these ophiolites and the fluids circulating through them. This disequilibrium represents a potential source of chemical energy that could sustain life. Moreover, E (h)-pH conditions resulting from rock- water interactions in ultrabasic rocks are conducive to important abiotic processes antecedent to the origin of life. Serpentinization--the reaction of olivine- and pyroxene-rich rocks with water--produces magnetite, hydroxide, and serpentine minerals, and liberates molecular hydrogen, a source of energy and electrons that can be readily utilized by a broad array of chemosynthetic organisms. These systems are viewed as important analogs for potential early ecosystems on both Earth and Mars, where highly reducing mineralogy was likely widespread in an undifferentiated crust. Secondary phases precipitated during serpentinization have the capability to preserve organic or mineral biosignatures. We describe the petrology and mineral chemistry of an ophiolite-hosted cold spring in northern California and propose criteria to aid in the identification of serpentinizing terranes on Mars that have the potential to harbor chemosynthetic life.     

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.     

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.     

Fluid inclusion studies of chemosynthetic carbonates: strategy for seeking life on Mars

Fluid inclusions in minerals hold the potential to provide important data on the chemistry of the ambient fluids during mineral precipitation. Especially interesting to astrobiologists are inclusions in low-temperature minerals that may have been precipitated in the presence of microorganisms. We demonstrate that it is possible to obtain data from inclusions in chemosynthetic carbonates that precipitated by the oxidation of organic carbon around methane-bearing seepages. Chemosynthetic carbonates have been identified as a target rock for astrobiological exploration. Other surficial rock types identified as targets for astrobiological exploration include hydrothermal deposits, speleothems, stromatolites, tufas, and evaporites, each of which can contain fluid inclusions. Fracture systems below impact craters would also contain precipitates of minerals with fluid inclusions. As fluid inclusions are sealed microchambers, they preserve fluids in regions where water is now absent, such as regions of the martian surface. Although most inclusions are < 5 microns, the possibility to obtain data from the fluids, including biosignatures and physical remains of life, underscores the advantages of technological advances in the study of fluid inclusions. The crushing of bulk samples could release inclusion waters for analysis, which could be undertaken in situ on Mars.     

A hydrothermal system associated with the Siljan impact structure, Sweden--implications for the search for fossil life on Mars

The Siljan ring structure (368 +/- 1.1 Ma) is the largest known impact structure in Europe. It isa 65-km-wide, eroded, complex impact structure, displaying several structural units, including a central uplifted region surrounded by a ring-shaped depression. Associated with the impact crater are traces of a post-impact hydrothermal system indicated by precipitated and altered hydrothermal mineral assemblages. Precipitated hydrothermal minerals include quartz veins and breccia fillings associated with granitic rocks at the outer margin of the central uplift, and calcite, fluorite, galena, and sphalerite veins associated with Paleozoic carbonate rocks located outside the central uplift. Two-phase water/gas and oil/gas inclusions in calcite and fluorite display homogenization temperatures between 75 degrees C and 137 degrees C. With an estimated erosional unloading of approximately 1 km, the formation temperatures were probably not more than 10-15 degrees C higher. Fluid inclusion ice-melting temperatures indicate a very low salt content, reducing the probability that the mineralization was precipitated during the Caledonian Orogeny. Our findings suggest that large impacts induce low-temperature hydrothermal systems that may be habitats for thermophilic organisms. Large impact structures on Mars may therefore be suitable targets in the search for fossil thermophilic organisms.     

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

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

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.     

Hydrogeologic controls on episodic H2 release from precambrian fractured rocks--energy for deep subsurface life on earth and mars

Dissolved H(2) concentrations up to the mM range and H(2) levels up to 9-58% by volume in the free gas phase are reported for groundwaters at sites in the Precambrian shields of Canada and Finland. Along with previously reported dissolved H(2) concentrations up to 7.4 mM for groundwaters from the Witwatersrand Basin, South Africa, these findings indicate that deep Precambrian Shield fracture waters contain some of the highest levels of dissolved H(2) ever reported and represent a potentially important energy-rich environment for subsurface microbial life. The delta (2)H isotope signatures of H(2) gas from Canada, Finland, and South Africa are consistent with a range of H(2)-producing water-rock reactions, depending on the geologic setting, which include both serpentinization and radiolysis. In Canada and Finland, several of the sites are in Archean greenstone belts characterized by ultramafic rocks that have under-gone serpentinization and may be ancient analogues for serpentinite-hosted gases recently reported at the Lost City Hydrothermal Field and other hydrothermal seafloor deposits. The hydrogeologically isolated nature of these fracture-controlled groundwater systems provides a mechanism whereby the products of water-rock interaction accumulate over geologic timescales, which produces correlations between high H(2) levels, abiogenic hydrocarbon signatures, and the high salinities and highly altered delta (18)O and delta (2)H values of these groundwaters. A conceptual model is presented that demonstrates how periodic opening of fractures and resultant mixing control the distribution and supply of H(2) and support a microbial community of H(2)-utilizing sulfate reducers and methanogens.     

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.     

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.     

Strategy for modeling putative multilevel ecosystems on Europa

A general strategy for modeling ecosystems on other worlds is described. Two alternative biospheres beneath the ice surface of Europa are modeled, based on analogous ecosystems on Earth in potentially comparable habitats, with reallocation of biomass quantities consistent with different sources of energy and chemical constituents. The first ecosystem models a benthic biosphere supported by chemoautotrophic producers. The second models two concentrations of biota at the top and bottom of the subsurface water column supported by energy harvested from transmembrane ionic gradients. Calculations indicate the plausibility of both ecosystems, including small macroorganisms at the highest trophic levels, with ionotrophy supporting a larger biomass than chemoautotrophy.     

DSC对苯基苯酚改性酚醛树脂固化机理研究

采用DSC技术、Kissinger法对苯基苯酚改性酚醛树脂的固化过程进行了研究,得到放热峰顶活化能为169.3 kJ/mol,远大于普通酚醛树脂(约70 kJ/mol)。理论近似凝胶温度、固化温度及后处理温度分别为414.5 K、448.9 K和483.9K。酚醛树脂的固化通常由化学反应控制和扩散控制两阶段组成。通过Ozawa法得到活化能与转化率(E-a)的变化关系表明,2种树脂固化历程存在明显差异。普通酚醛树脂固化反应进行到10%(a=10%),粘度迅速增大,反应转向扩散控制;而苯基苯酚改性酚醛树脂固化反应时粘度变化小,直至a=70%,才较快增长。这将有利于小分子的逃逸和各基团充分反应。同时高活化能也表明,反应形成了高键能的化学键,有利于提高树脂的残炭率和烧蚀性能。     

Formate as an energy source for microbial metabolism in chemosynthetic zones of hydrothermal ecosystems

Formate, a simple organic acid known to support chemotrophic hyperthermophiles, is found in hot springs of varying temperature and pH. However, it is not yet known how metabolic strategies that use formate could contribute to primary productivity in hydrothermal ecosystems. In an effort to provide a quantitative framework for assessing the role of formate metabolism, concentration data for dissolved formate and many other solutes in samples from Yellowstone hot springs were used, together with data for coexisting gas compositions, to evaluate the overall Gibbs energy for many reactions involving formate oxidation or reduction. The result is the first rigorous thermodynamic assessment of reactions involving formate oxidation to bicarbonate and reduction to methane coupled with various forms of iron, nitrogen, sulfur, hydrogen, and oxygen for hydrothermal ecosystems. We conclude that there are a limited number of reactions that can yield energy through formate reduction, in contrast to numerous formate oxidation reactions that can yield abundant energy for chemosynthetic microorganisms. Because the energy yields are so high, these results challenge the notion that hydrogen is the primary energy source of chemosynthetic microbes in hydrothermal ecosystems.     

Carotenoid analysis of halophilic archaea by resonance Raman spectroscopy

Recently, halite and sulfate evaporate rocks have been discovered on Mars by the NASA rovers, Spirit and Opportunity. It is reasonable to propose that halophilic microorganisms could have potentially flourished in these settings. If so, biomolecules found in microorganisms adapted to high salinity and basic pH environments on Earth may be reliable biomarkers for detecting life on Mars. Therefore, we investigated the potential of Resonance Raman (RR) spectroscopy to detect biomarkers derived from microorganisms adapted to hypersaline environments. RR spectra were acquired using 488.0 and 514.5 nm excitation from a variety of halophilic archaea, including Halobacterium salinarum NRC-1, Halococcus morrhuae, and Natrinema pallidum. It was clearly demonstrated that RR spectra enhance the chromophore carotenoid molecules in the cell membrane with respect to the various protein and lipid cellular components. RR spectra acquired from all halophilic archaea investigated contained major features at approximately 1000, 1152, and 1505 cm(-1). The bands at 1505 cm(-1) and 1152 cm(-1) are due to in-phase C=C (nu(1) ) and C-C stretching ( nu(2) ) vibrations of the polyene chain in carotenoids. Additionally, in-plane rocking modes of CH(3) groups attached to the polyene chain coupled with C-C bonds occur in the 1000 cm(-1) region. We also investigated the RR spectral differences between bacterioruberin and bacteriorhodopsin as another potential biomarker for hypersaline environments. By comparison, the RR spectrum acquired from bacteriorhodopsin is much more complex and contains modes that can be divided into four groups: the C=C stretches (1600-1500 cm(-1)), the CCH in-plane rocks (1400-1250 cm(-1)), the C-C stretches (1250-1100 cm(-1)), and the hydrogen out-of-plane wags (1000-700 cm(-1)). RR spectroscopy was shown to be a useful tool for the analysis and remote in situ detection of carotenoids from halophilic archaea without the need for large sample sizes and complicated extractions, which are required by analytical techniques such as high performance liquid chromatography and mass spectrometry.