Geochemical constraints on sources of metabolic energy for chemolithoautotrophy in ultramafic-hosted deep-sea hydrothermal systems

Numerical models are employed to investigate sources of chemical energy for autotrophic microbial metabolism that develop during mixing of oxidized seawater with strongly reduced fluids discharged from ultramafic-hosted hydrothermal systems on the seafloor. Hydrothermal fluids in these systems are highly enriched in H(2) and CH(4) as a result of alteration of ultramafic rocks (serpentinization) in the subsurface. Based on the availability of chemical energy sources, inferences are made about the likely metabolic diversity, relative abundance, and spatial distribution of microorganisms within ultramafic-hosted systems. Metabolic reactions involving H(2) and CH(4), particularly hydrogen oxidation, methanotrophy, sulfate reduction, and methanogenesis, represent the predominant sources of chemical energy during fluid mixing. Owing to chemical gradients that develop from fluid mixing, aerobic metabolisms are likely to predominate in low-temperature environments (<20-30 degrees C), while anaerobes will dominate higher-temperature environments. Overall, aerobic metabolic reactions can supply up to approximately 7 kJ of energy per kilogram of hydrothermal fluid, while anaerobic metabolic reactions can supply about 1 kJ, which is sufficient to support a maximum of approximately 120 mg (dry weight) of primary biomass production by aerobic organisms and approximately 20-30 mg biomass by anaerobes. The results indicate that ultramafic-hosted systems are capable of supplying about twice as much chemical energy as analogous deep-sea hydrothermal systems hosted in basaltic rocks.     

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.     

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.     

Nitrogen reduction under hydrothermal vent conditions: implications for the prebiotic synthesis of C-H-O-N compounds

Dinitrogen is reduced in dilute hydrogen sulfide (H2S) solutions to ammonium at 120 degrees C. Experiments with dissolved dinitrogen (partial pressure 50 bar) in a 12 x 10(-3) mol/L H2S(aq) solution yield approximately 10(-5) mol/L NH4+ within 2-7 days. These yields are consistent with the equilibrium NH4+ concentration for the N-S-H system under these conditions. The formation of ammonium is catalyzed by the presence of freshly precipitated iron monosulfide. These results indicate that dinitrogen can be reduced at moderate temperatures in hydrothermal vent systems. Abiotic nitrogen reduction could have taken place within primordial hydrothermal vents, supplying some ammonia for the synthesis of C-H-O-N compounds via abiotic processes. The yield of ammonia via dinitrogen reduction by hydrogen sulfide, however, is so low that it is doubtful this process could have produced enough ammonia to sustain prebiotic hydrothermal synthesis of C-H-O-N compounds in or around vent systems.     

Sulfur-oxidizing chemolithotrophic proteobacteria dominate the microbiota in high arctic thermal springs on Svalbard

The thermal springs Trollosen and Fisosen, located on the High Arctic archipelago Svalbard, discharge saline groundwaters rich in hydrogen sulfide and ammonium through a thick layer of permafrost. Large amounts of biomass that consist of filamentous microorganisms containing sulfur granules, as analyzed with energy dispersive X-ray analysis, were found in the outflow. Prokaryotic 16S rRNA gene libraries and quantitative polymerase chain reaction (qPCR) analyses reported bacteria of the γ- and ?-proteobacterial classes as the dominant organisms in the filaments and the planktonic fractions, closely related to known chemolithoautotrophic sulfur oxidizers (Thiotrix and Sulfurovum). Archaea comprised ～1% of the microbial community, with the majority of sequences affiliated with the Thaumarchaeota. Archaeal and bacterial genes coding for a subunit of the enzyme ammonia monooxygenase (amoA) were detected, as well as 16S?rRNA genes of Nitrospira, all of which is indicative of potential complete nitrification in both springs. 16S rRNA sequences related to methanogens and methanotrophs were detected as well. This study provides evidence that the microbial communities in Trollosen and Fisosen are sustained by chemolithotrophy, mainly through the oxidation of reduced sulfur compounds, and that ammonium and methane might be minor, additional sources of energy and carbon.     

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.     

Hydrothermal systems in small ocean planets

We examine means for driving hydrothermal activity in extraterrestrial oceans on planets and satellites of less than one Earth mass, with implications for sustaining a low level of biological activity over geological timescales. Assuming ocean planets have olivine-dominated lithospheres, a model for cooling-induced thermal cracking shows how variation in planet size and internal thermal energy may drive variation in the dominant type of hydrothermal system-for example, high or low temperature system or chemically driven system. As radiogenic heating diminishes over time, progressive exposure of new rock continues to the current epoch. Where fluid-rock interactions propagate slowly into a deep brittle layer, thermal energy from serpentinization may be the primary cause of hydrothermal activity in small ocean planets. We show that the time-varying hydrostatic head of a tidally forced ice shell may drive hydrothermal fluid flow through the seafloor, which can generate moderate but potentially important heat through viscous interaction with the matrix of porous seafloor rock. Considering all presently known potential ocean planets-Mars, a number of icy satellites, Pluto, and other trans-neptunian objects-and applying Earth-like material properties and cooling rates, we find depths of circulation are more than an order of magnitude greater than in Earth. In Europa and Enceladus, tidal flexing may drive hydrothermal circulation and, in Europa, may generate heat on the same order as present-day radiogenic heat flux at Earth's surface. In all objects, progressive serpentinization generates heat on a globally averaged basis at a fraction of a percent of present-day radiogenic heating and hydrogen is produced at rates between 10(9) and 10(10) molecules cm(2) s(1).     

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.     

The possible origin and persistence of life on Enceladus and detection of biomarkers in the plume

The jets of icy particles and water vapor issuing from the south pole of Enceladus are evidence for activity driven by some geophysical energy source. The vapor has also been shown to contain simple organic compounds, and the south polar terrain is bathed in excess heat coming from below. The source of the ice and vapor, and the mechanisms that accelerate the material into space, remain obscure. However, it is possible that a liquid water environment exists beneath the south polar cap, which may be conducive to life. Several theories for the origin of life on Earth would apply to Enceladus. These are (1) origin in an organic-rich mixture, (2) origin in the redox gradient of a submarine vent, and (3) panspermia. There are three microbial ecosystems on Earth that do not rely on sunlight, oxygen, or organics produced at the surface and, thus, provide analogues for possible ecologies on Enceladus. Two of these ecosystems are found deep in volcanic rock, and the primary productivity is based on the consumption by methanogens of hydrogen produced by rock reactions with water. The third ecosystem is found deep below the surface in South Africa and is based on sulfur-reducing bacteria consuming hydrogen and sulfate, both of which are ultimately produced by radioactive decay. Methane has been detected in the plume of Enceladus and may be biological in origin. An indicator of biological origin may be the ratio of non-methane hydrocarbons to methane, which is very low (0.001) for biological sources but is higher (0.1-0.01) for nonbiological sources. Thus, Cassini's instruments may detect plausible evidence for life by analysis of hydrocarbons in the plume during close encounters.     

Biogeochemistry of hypersaline springs supporting a mid-continent marine ecosystem: an analogue for martian springs?

Hypersaline springs that host unique mid-continent marine ecosystems were examined in central Manitoba, Canada. The springs originate from a reflux of glacial meltwater that intrudes into underlying bedrock and dissolved buried salt beds. Two spring types were distinguished based both on flow rate and geochemistry. High flow springs (greater than 10 L/s) hosted extensive marine microbial mats, which were dominated by algae but also included diverse microbes. These varied somewhat between springs as indicated by changes in profiles of fatty acid methyl esters. Culture studies confirmed the presence of sulfate-reducing bacteria in sediments at the high flow sites. In contrast, low flow springs were affected by solar evaporation, increasing salinity, and temperature. These low flow springs behaved more like closed nutrient-limited systems and did not support microbial mats. Direct comparison of the high and low flow springs revealed interesting implications for the potential to record biosignatures in the rock record. High flow springs have abundant, well-developed microbial mats, which desiccate and are cemented along the edges of the spring pools; however, the high mass flux overwhelms any geochemical signature of microbial activity. In contrast, the nutrient-limited low flow sites develop strong geochemical signatures of sulfate reduction, even in the absence of microbial mats, due to less dilution with the lower flows. Geochemical and physical evidence for life did not correlate with the abundance of microbial life but, rather, with the extent to which the biological system formed a closed ecosystem.     

Hydrogen cyanide polymerization: a preferred cosmochemical pathway

Current research in cosmochemistry shows that crude organic solids of high molecular weight are readily formed in planetary, interplanetary and interstellar environments. Underlying much of this ubiquitous chemistry is a low energy route leading directly to the synthesis of hydrogen cyanide and its polymers. Evidence from laboratory and extraterrestrial investigations suggests that these polymers plus water yield heteropolypeptides, a truly universal process that accounts not only for the past synthesis of protein ancestors on Earth but also for reactions proceeding elsewhere today within our solar system, on planetary bodies and satellites around other stars and in the dusty molecular clouds of spiral galaxies. The existence of this preferred pathway - hydrogen cyanide polymerization - surely increases greatly the probability that carbon-based life is widespread in the universe.     

Supraglacial sulfur springs and associated biological activity in the Canadian high arctic-signs of life beneath the ice

Unique springs, discharging from the surface of an arctic glacier, release H(2)S and deposit native sulfur, gypsum, and calcite. The presence of sulfur in three oxidation states indicates a complex series of redox reactions. Physical and chemical conditions of the spring water and surrounding environment, as well as mineralogical and isotopic signatures, suggest biologically mediated reactions. Cell counts and DNA analyses confirm bacteria are present in the spring system, and a limited number of sequenced isolates suggests that complex communities of bacteria live within the glacial system.     

Complex morphological variability in complex evaporitic systems: thermal spring snails from the Chihuahuan Desert, Mexico

Thermal springs in evaporitic environments provide a unique biological laboratory in which to study natural selection and evolutionary diversification. These isolated systems may be an analogue for conditions in early Earth or Mars history. One modern example of such a system can be found in the Chihuahuan Desert of north-central Mexico. The Cuatro Cienegas basin hosts a series of thermal springs that form a complex of aquatic ecosystems under a range of environmental conditions. Using landmark-based morphometric techniques, we have quantified an unusually high level of morphological variability in the endemic gastropod Mexipyrgus from Cuatro Cienegas. The differentiation is seen both within and between hydrological systems. Our results suggest that this type of environmental system is capable of producing and maintaining a high level of morphological diversity on small spatial scales, and thus should be a target for future astrobiological research.     

Hydrothermal simulation experiments as a tool for studies of the origin of life on Earth and other terrestrial planets: a review

The potential of life's origin in submarine hydrothermal systems has been evaluated by a number of investigators by conducting high temperature-high pressure experiments involving organic compounds. In the majority of these experiments little attention has been paid to the importance of constraining important parameters, such as the pH and the redox state of the system. This is particularly revealed in the apparent difficulties in interpreting experimental data from hydrothermal organic synthesis and stability studies. However, in those cases where common mineral assemblages have been used in an attempt to buffer the pH and redox conditions to geologically and geochemically realistic values, theoretical and experimental data seem to converge. The use of mineral buffer assemblages provides a convenient way by which to constrain the experimental conditions. Studies at high temperatures and pressure in the laboratory have revealed a number of reactions that proceed rapidly in hydrothermal fluids, including the Strecker synthesis of amino acids. In other cases, the verification of postulated abiotic reaction mechanisms has not been possible, at least for large molecules such as large fatty acids and hydrocarbons. This includes the Fischer-Tropsch synthesis reaction. High temperature-high pressure experimental methods have been developed and used successfully for a long time in, for example, mineral solubility studies under hydrothermal conditions. By taking advantage of this experimental experience new and, at times, unexpected directions can be taken in bioorganic geochemistry, one being, for instance, primitive two-dimensional information coding. This article critically reviews some of the organic synthesis and stability experiments that have been conducted under simulated submarine hydrothermal conditions. We also discuss some of the theoretical and practical considerations that apply to hydrothermal laboratory studies of organic molecules related to the origin of life on Earth and probably also to the other terrestrial planets.     

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.     

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.     

FeS/S/FeS(2) redox system and its oxidoreductase-like chemistry in the iron-sulfur world

The iron-sulfur world (ISW) theory is an intriguing prediction regarding the origin of life on early Earth. It hypothesizes that life arose as a geochemical process from inorganic starting materials on the surface of sulfide minerals in the vicinity of deep-sea hot springs. During the last two decades, many experimental studies have been carried out on this topic, and some interesting results have been achieved. Among them, however, the processes of carbon/nitrogen fixation and biomolecular assembly on the mineral surface have received an inordinate amount of attention. To the present, an abiotic model for the oxidation-reduction of intermediates participating in metabolic pathways has been ignored. We examined the oxidation-reduction effect of a prebiotic FeS/S/FeS(2) redox system on the interconversion between several pairs of α-hydroxy acids and α-keto acids (i.e., lactate/pyruvate, malate/oxaloacetate, and glycolate/glyoxylate). We found that, in the absence of FeS, elemental sulfur (S) oxidized α-hydroxy acids to form corresponding keto acids only at a temperature higher than its melting point (113°C); in the presence of FeS, such reactions occurred more efficiently through a coupled reaction mechanism, even at a temperature below the phase transition point of S. On the other hand, FeS was shown to have the capacity to reversibly reduce the keto acids. Such an oxidoreductase-like chemistry of the FeS/S/FeS(2) redox system suggests that it can determine the redox homeostasis of metabolic intermediates in the early evolutionary phase of life. The results provide a possible pathway for the development of primordial redox biochemistry in the iron-sulfur world. Key Words: Iron-sulfur world-FeS/S/FeS(2) redox system-Oxidoreductase-like chemistry. Astrobiology 11, 471-476.     

我国大推力补燃氢氧发动机研究进展

氢氧火箭发动机因具有很高的性能,在国内外运载火箭中得到了广泛应用。为了更好地开展深空探测,必须研制大推力氢氧火箭发动机。本文综合分析了国内外氢氧发动机的发展历史和现状,简要介绍了我国220 t补燃循环氢氧发动机方案和关键技术研制进展,该技术方案先进。通过开展试验件冷态试验和缩尺组件热试验等,研究了核心部组件的关键技术和方案选型。开展全尺寸预燃室热试验等分系统热试验,研究组件级技术,初步突破了部分关键技术。建议加快开展大推力氢氧发动机工程研制,促进我国航天推进技术发展。     

Radiolytic hydrogen and microbial respiration in subsurface sediments

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