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1.
Geobiology ; 11(6): 549-69, 2013 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-23981055

RESUMO

Detailed analysis of 16S rRNA and intact polar lipids (IPLs) from streamer biofilm communities (SBCs), collected from geochemically similar hot springs in the Lower Geyser Basin, Yellowstone National Park, shows good agreement and affirm that IPLs can be used as reliable markers for the microbial constituents of SBCs. Uncultured Crenarchaea are prominent in SBS, and their IPLs contain both glycosidic and mixed glyco-phospho head groups with tetraether cores, having 0-4 rings. Archaeal IPL contributions increase with increasing temperature and comprise up to one-fourth of the total IPL inventory at >84 °C. At elevated temperatures, bacterial IPLs contain abundant glycosidic glycerol diether lipids. Diether and diacylglycerol (DAG) lipids with aminopentanetetrol and phosphatidylinositol head groups were identified as lipids diagnostic of Aquificales, while DAG glycolipids and glyco-phospholipids containing N-acetylgycosamine as head group were assigned to members of the Thermales. With decreasing temperature and concomitant changes in water chemistry, IPLs typical of phototrophic bacteria, such as mono-, diglycosyl, and sulfoquinovosyl DAG, which are specific for cyanobacteria, increase in abundance, consistent with genomic data from the same samples. Compound-specific stable carbon isotope analysis of IPL breakdown products reveals a large isotopic diversity among SBCs in different hot springs. At two of the hot springs, 'Bison Pool' and Flat Cone, lipids derived from Aquificales are enriched in (13) C relative to biomass and approach values close to dissolved inorganic carbon (DIC) (approximately 0‰), consistent with fractionation during autotrophic carbon fixation via the reversed tricarboxylic acid pathway. At a third site, Octopus Spring, the same Aquificales-diagnostic lipids are 10‰ depleted relative to biomass and resemble stable carbon isotope values of dissolved organic carbon (DOC), indicative of heterotrophy. Other bacterial and archaeal lipids show a similar variance, with values resembling the DIC or DOC pool or a mixture thereof. This variance cannot be explained by hot spring chemistry or temperature alone, but instead, we argue that intermittent input of exogenous organic carbon can result in metabolic shifts of the chemotrophic communities from autotrophy to heterotrophy and vice versa.


Assuntos
Archaea/classificação , Archaea/genética , Bactérias/classificação , Bactérias/genética , Biofilmes , Biota , Fontes Termais/microbiologia , Análise por Conglomerados , DNA Arqueal/química , DNA Arqueal/genética , DNA Bacteriano/química , DNA Bacteriano/genética , DNA Ribossômico/química , DNA Ribossômico/genética , Genes de RNAr , Lipídeos/análise , Dados de Sequência Molecular , Filogenia , RNA Arqueal/genética , RNA Bacteriano/genética , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , Homologia de Sequência do Ácido Nucleico , Temperatura , Estados Unidos
2.
Astrobiology ; 13(8): 740-73, 2013 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-23924246

RESUMO

The prospect of a future soft landing on the surface of Europa is enticing, as it would create science opportunities that could not be achieved through flyby or orbital remote sensing, with direct relevance to Europa's potential habitability. Here, we summarize the science of a Europa lander concept, as developed by our NASA-commissioned Science Definition Team. The science concept concentrates on observations that can best be achieved by in situ examination of Europa from its surface. We discuss the suggested science objectives and investigations for a Europa lander mission, along with a model planning payload of instruments that could address these objectives. The highest priority is active sampling of Europa's non-ice material from at least two different depths (0.5-2 cm and 5-10 cm) to understand its detailed composition and chemistry and the specific nature of salts, any organic materials, and other contaminants. A secondary focus is geophysical prospecting of Europa, through seismology and magnetometry, to probe the satellite's ice shell and ocean. Finally, the surface geology can be characterized in situ at a human scale. A Europa lander could take advantage of the complex radiation environment of the satellite, landing where modeling suggests that radiation is about an order of magnitude less intense than in other regions. However, to choose a landing site that is safe and would yield the maximum science return, thorough reconnaissance of Europa would be required prior to selecting a scientifically optimized landing site.


Assuntos
Exobiologia , Geologia , Júpiter , Voo Espacial , Oceanos e Mares
3.
Extremophiles ; 16(2): 317-31, 2012 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-22311159

RESUMO

The majority of microorganisms in natural environments resist laboratory cultivation. Sometimes referred to as 'unculturable', many phylogenetic groups are known only by fragments of recovered DNA. As a result, the ecological significance of whole branches of the 'tree of life' remains a mystery; this is particularly true when regarding genetic material retrieved from extreme environments. Geochemically relevant media have been used to improve the success of culturing Archaea and Bacteria, but these efforts have focused primarily on optimizing pH, alkalinity, major ions, carbon sources, and electron acceptor-donor pairs. Here, we cultured thermophilic microorganisms from 'Sylvan Spring' (Yellowstone National Park, USA) on media employing different trace element solutions, including one that mimicked the source fluid of the inocula. The growth medium that best simulated trace elements found in 'Sylvan Spring' produced a more diverse and faster growing mixed culture than media containing highly elevated trace element concentrations. The elevated trace element medium produced fewer phylotypes and inhibited growth. Trace element concentrations appear to influence growth conditions in extreme environments. Incorporating geochemical data into cultivation attempts may improve culturing success.


Assuntos
Archaea/genética , Desulfurococcales/metabolismo , Oligoelementos/análise , Archaea/metabolismo , Carbono/química , Técnicas de Cultura de Células , Química/métodos , DNA/química , DNA/genética , Ecologia , Elétrons , Geologia/métodos , Concentração de Íons de Hidrogênio , Íons , Microscopia Eletrônica de Transmissão/métodos , Oxirredução , Filogenia , Sais/química , Temperatura , Fatores de Tempo , Wyoming
4.
Geobiology ; 8(2): 140-54, 2010 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-20002204

RESUMO

A culture-independent community census was combined with chemical and thermodynamic analyses of three springs located within the Long Valley Caldera, Little Hot Creek (LHC) 1, 3, and 4. All three springs were approximately 80 degrees C, circumneutral, apparently anaerobic and had similar water chemistries. 16S rRNA gene libraries constructed from DNA isolated from spring sediment revealed moderately diverse but highly novel microbial communities. Over half of the phylotypes could not be grouped into known taxonomic classes. Bacterial libraries from LHC1 and LHC3 were predominantly species within the phyla Aquificae and Thermodesulfobacteria, while those from LHC4 were dominated by candidate phyla, including OP1 and OP9. Archaeal libraries from LHC3 contained large numbers of Archaeoglobales and Desulfurococcales, while LHC1 and LHC4 were dominated by Crenarchaeota unaffiliated with known orders. The heterogeneity in microbial populations could not easily be attributed to measurable differences in water chemistry, but may be determined by availability of trace amounts of oxygen to the spring sediments. Thermodynamic modeling predicted the most favorable reactions to be sulfur and nitrate respirations, yielding 40-70 kJ mol(-1) e(-) transferred; however, levels of oxygen at or below our detection limit could result in aerobic respirations yielding up to 100 kJ mol(-1) e(-) transferred. Important electron donors are predicted to be H(2), H(2)S, S(0), Fe(2+) and CH(4), all of which yield similar energies when coupled to a given electron acceptor. The results indicate that springs associated with the Long Valley Caldera contain microbial populations that show some similarities both to springs in Yellowstone and springs in the Great Basin.


Assuntos
Archaea , Bactérias , Ecossistema , Fontes Termais , Archaea/classificação , Archaea/genética , Archaea/isolamento & purificação , Bactérias/classificação , Bactérias/genética , Bactérias/isolamento & purificação , California , DNA Arqueal/genética , DNA Arqueal/isolamento & purificação , DNA Bacteriano/genética , DNA Bacteriano/isolamento & purificação , Genes de RNAr , Sedimentos Geológicos/microbiologia , Fontes Termais/química , Fontes Termais/microbiologia , Dados de Sequência Molecular , Filogenia , RNA Ribossômico 16S/genética , Análise de Sequência de DNA , Termodinâmica
5.
Equine Vet J Suppl ; (36): 267-73, 2006 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-17402430

RESUMO

REASONS FOR PERFORMING STUDY: Ageing appears to affect immune and neuroendocirne function in horses and response to acute exercise. No studies have examined the combined effects of training and ageing on immune and neuroendocirne function in horses. HYPOTHESIS: To ascertain whether training and age would affect the plasma beta-endorphin (BE) and cortisol (C) as well as immune function responses to acute exercise in Standardbred mares. METHODS: Graded exercise tests (GXT) and simulated race tests (SRT) were performed before and after 12 weeks training at 60 % HRmax. BE and C were measured at rest and at 5, 10, 20, 40, 60 and 120 min post GXT. Leucocyte cell number, CD4+ and CD8+ lymphocyte subsets, and mitogen stimulated lymphoproliferative response (LPR), were measured in jugular blood before and after the SRTs. RESULTS: Cortisol rose by 5 min post GXT in young (Y) and middle-age (MA) mares (P<0.05) and remained elevated until 40 and 60 min post GXT, respectively during both pre- and post training GXT. There was no rise in C in old (0) mares after either GXT (P>0.05). Pretraining BE rose (P<0.05) by 5 min post GXT in all mares. After training, BE was higher in Y and O vs. MA (P<0.05) at 5 min post GXT. Post training BE was higher at 5 min post GXT in Y and O vs. pretraining (P<0.05). After SRT, lymphocyte number rose in all mares (P<0.05); however, lower lymphocyte numbers (P<0.05) were seen in MA vs. Y and O vs. MA (P<0.05). The O had reduced LPR to Con A and PHA stimulation (P<0.05) compared to Y and MA after the SRT after both pre- and post training SRT. LPR to PWM was lower (P<0.05) in O vs. Y and MA after the pretraining SRT. Training caused an increase in resting LPR to PWM in MA only (P<0.05). CONCLUSION: Both age and training altered the plasma beta-endorphin and cortisol responses as well as and immune responses to acute exercise. POTENTIAL RELEVANCE: This study provides important information on the effects of ageing and training that will aid in the management and care of an increasing number of active older horses.


Assuntos
Envelhecimento/fisiologia , Cavalos , Hidrocortisona/sangue , Condicionamento Físico Animal , beta-Endorfina/sangue , Fatores Etários , Envelhecimento/imunologia , Animais , Área Sob a Curva , Contagem de Linfócito CD4/veterinária , Relação CD4-CD8/veterinária , Teste de Esforço/veterinária , Cavalos/sangue , Cavalos/imunologia , Cavalos/fisiologia , Contagem de Leucócitos/veterinária , Mitógenos/farmacologia , Condicionamento Físico Animal/métodos , Condicionamento Físico Animal/fisiologia
6.
FEMS Microbiol Rev ; 25(2): 175-243, 2001 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-11250035

RESUMO

Thermophilic and hyperthermophilic Archaea and Bacteria have been isolated from marine hydrothermal systems, heated sediments, continental solfataras, hot springs, water heaters, and industrial waste. They catalyze a tremendous array of widely varying metabolic processes. As determined in the laboratory, electron donors in thermophilic and hyperthermophilic microbial redox reactions include H2, Fe(2+), H2S, S, S2O3(2-), S4O6(2-), sulfide minerals, CH4, various mono-, di-, and hydroxy-carboxylic acids, alcohols, amino acids, and complex organic substrates; electron acceptors include O2, Fe(3+), CO2, CO, NO3(-), NO2(-), NO, N2O, SO4(2-), SO3(2-), S2O3(2-), and S. Although many assimilatory and dissimilatory metabolic reactions have been identified for these groups of microorganisms, little attention has been paid to the energetics of these reactions. In this review, standard molal Gibbs free energies (DeltaGr(0)) as a function of temperature to 200 degrees C are tabulated for 370 organic and inorganic redox, disproportionation, dissociation, hydrolysis, and solubility reactions directly or indirectly involved in microbial metabolism. To calculate values of DeltaGr(0) for these and countless other reactions, the apparent standard molal Gibbs free energies of formation (DeltaG(0)) at temperatures to 200 degrees C are given for 307 solids, liquids, gases, and aqueous solutes. It is shown that values of DeltaGr(0) for many microbially mediated reactions are highly temperature dependent, and that adopting values determined at 25 degrees C for systems at elevated temperatures introduces significant and unnecessary errors. The metabolic processes considered here involve compounds that belong to the following chemical systems: H-O, H-O-N, H-O-S, H-O-N-S, H-O-C(inorganic), H-O-C, H-O-N-C, H-O-S-C, H-O-N-S-C(amino acids), H-O-S-C-metals/minerals, and H-O-P. For four metabolic reactions of particular interest in thermophily and hyperthermophily (knallgas reaction, anaerobic sulfur and nitrate reduction, and autotrophic methanogenesis), values of the overall Gibbs free energy (DeltaGr) as a function of temperature are calculated for a wide range of chemical compositions likely to be present in near-surface and deep hydrothermal and geothermal systems.


Assuntos
Archaea/metabolismo , Bactérias/metabolismo , Metabolismo Energético , Microbiologia Ambiental , Modelos Químicos , Oxirredução , Temperatura , Termodinâmica
7.
J Geophys Res ; 105(B1): 539-59, 2000 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-11543291

RESUMO

The possibility for abiotic synthesis of condensed hydrocarbons in cooling/diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous CO, CO2, H2 and H2O. The stabilities of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) have been evaluated for several typical volcanic gas compositions under various conditions for cooling/diluting of quenched volcanic gas. The modeling shows that n-alkanes and PAHs have a thermodynamic potential to form metastably from H2 and CO below approximately 250 degrees C within the stability field of graphite. Despite the predominance of CO2 in volcanic gases, synthesis of hydrocarbons from CO2 and H2 is less favored energetically than from CO and H2. Both low temperature and a high H/C atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher H/C ratios. PAHs are thermodynamically stable at temperatures approximately 10 degrees -50 degrees C higher than large n-alkanes; however, at lower temperatures, PAHs and n-alkanes have similar stabilities and are likely to form metastable mixtures. Both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state (fO2) of the volcanic gases decreases and as the cooling/dilution ratios of volcanic gases increase. Synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns. Mechanisms for hydrocarbon formation may include Fischer-Tropsch-type synthesis catalyzed by magnetite from solid volcanic products. On the early Earth, Mars, and Jupiter's satellite Europa, several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life.


Assuntos
Alcanos/síntese química , Evolução Química , Hidrocarbonetos/síntese química , Hidrocarbonetos Policíclicos Aromáticos/síntese química , Erupções Vulcânicas/análise , Dióxido de Carbono/química , Monóxido de Carbono/química , Planeta Terra , Evolução Planetária , Hidrogênio/química , Oxirredução , Planetas , Temperatura , Água/química
8.
Meteorit Planet Sci ; 35(3): 629-38, 2000 May.
Artigo em Inglês | MEDLINE | ID: mdl-11543519

RESUMO

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.


Assuntos
Alcanos/síntese química , Marte , Meteoroides , Modelos Químicos , Hidrocarbonetos Policíclicos Aromáticos/síntese química , Dióxido de Carbono/química , Monóxido de Carbono/química , Carbonatos/química , Exobiologia , Gases/química , Hidrogênio/química , Termodinâmica , Erupções Vulcânicas
9.
Energy Fuels ; 13(2): 401-10, 1999.
Artigo em Inglês | MEDLINE | ID: mdl-11762446

RESUMO

Polycyclic aromatic hydrocarbons (PAH) are found at high concentrations in thermally altered organic matter and hydrothermally generated petroleum from sediment-covered seafloor hydro-thermal systems. To better understand the factors controlling the occurrence of PAH in thermally altered environments, the reactivities of two PAH, phenanthrene and anthracene, were investigated in hydrothermal experiments. The compounds were heated with water at 330 degrees C in sealed reaction vessels for durations ranging from 1 to 17 days. Iron oxide and sulfide minerals, formic acid, or sodium for-mate were included in some experiments to vary conditions within the reaction vessel. Phenanthrene was unreactive both in water alone and in the presence of minerals for up to 17 days, while anthracene was partially hydrogenated (5-10%) to di- and tetrahydroanthracene. In the presence of 6-21 vol % formic acid, both phenanthrene and anthracene reacted extensively to form hydrogenated and minor methylated derivatives, with the degree of hydrogenation and methylation increasing with the amount of formic acid. Phenanthrene was slightly hydrogenated in sodium formate solutions. The hydrogenation reactions could be readily reversed; heating a mixture of polysaturated phenanthrenes resulted in extensive dehydrogenation (aromatization) after 3 days at 330 degrees C. While the experiments demonstrate that reaction pathways for the hydrogenation of PAH under hydrothermal conditions exist, the reactions apparently require higher concentrations of H2 than are typical of geologic settings. The experiments provide additional evidence that PAH may be generated in hydrothermal systems from progressive aromatization and dealkylation of biologically derived polycyclic precursors such as steroids and terpenoids. Furthermore, the results indicate that PAH initially present in sediments or formed within hydrothermal systems are resistant to further thermal degradation during hydrothermal alteration.


Assuntos
Antracenos/química , Temperatura Alta , Petróleo , Fenantrenos/química , Água , Compostos Férricos/química , Formiatos/química , Sedimentos Geológicos/química , Hidrogenação , Metilação , Oceanos e Mares , Hidrocarbonetos Policíclicos Aromáticos/química , Sulfetos/química , Fatores de Tempo
10.
J Chem Thermodyn ; 31(9): 1195-229, 1999 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-11543305

RESUMO

Densities of dilute aqueous solutions of isopropanol, 1,5-pentanediol, cyclohexanol, benzyl alcohol, diethyl ether, 1,2-dimethoxyethane, acetone, and 2,5-hexanedione were measured by means of a vibrating-tube flow densimeter at temperatures near T = (302, 373, 423, 473, and 521) K at a pressure of p = 28 MPa. At the lowest and highest temperatures, measurements were also made close to the saturation vapour pressure of water to investigate the effect of pressure on the volumes of solutes. Apparent molar volumes were calculated for each solute and extrapolated to give partial molar volumes at infinite dilution. The variation of the volume with temperature, pressure, and structure of solute is discussed qualitatively, and group contributions are determined at the temperatures of measurements and p = 28 MPa. Several equations proposed in the literature for correlating the partial molar volumes at infinite dilution as a function of state parameters are tested. Parameters of one selected equation are tabulated allowing calculation of the partial molar volumes at infinite dilution at temperatures and pressures up to T = 573 K and p = 40 MPa. respectively.


Assuntos
Álcoois/química , Éteres/química , Cetonas/química , Soluções/química , Termodinâmica , 2-Propanol/química , Acetona/química , Pressão Atmosférica , Álcool Benzílico/química , Cicloexanóis/química , Éter/química , Etil-Éteres/química , Glicóis/química , Hexanonas/química , Pentanos , Temperatura
11.
Science ; 281(5383): 1659-62, 1998 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-9733509

RESUMO

Thermodynamic calculations showed that the autotrophic synthesis of all 20 protein-forming amino acids was energetically favored in hot (100 degrees C), moderately reduced, submarine hydrothermal solutions relative to the synthesis in cold (18 degrees C), oxidized, surface seawater. The net synthesis reactions of 11 amino acids were exergonic in the hydrothermal solution, but all were endergonic in surface seawater. The synthesis of the requisite amino acids of nine thermophilic and hyperthermophilic proteins in a 100 degreesC hydrothermal solution yielded between 600 and 8000 kilojoules per mole of protein, which is energy that is available to drive the intracellular synthesis of enzymes and other biopolymers in hyperthermophiles thriving in these ecosystems.


Assuntos
Aminoácidos/biossíntese , Archaea/metabolismo , Bactérias/metabolismo , Ecossistema , Temperatura Alta , Oxirredução , Biossíntese de Proteínas , Água do Mar/microbiologia , Termodinâmica
12.
J Geophys Res ; 103(E8): 19359-64, 1998 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-11542257

RESUMO

The potential biomass that could have existed on Mars is constrained by the total amount of energy available to construct it. From an inventory of the available geochemical sources of energy, we estimate that from the time of the onset of the visible geologic record 4 b.y. ago to the present, as much as 20 g cm-2 of biota could have been created. This is the same amount that could have been constructed on the early Earth in only 100 million years. This indicates that there likely was sufficient energy available to support an origin of life on Mars but not sufficient energy to create a ubiquitous and lush biosphere. Similar calculations for Europa suggest that even less would have been available there.


Assuntos
Planeta Terra , Evolução Planetária , Exobiologia , Júpiter , Marte , Biomassa , Fontes Geradoras de Energia , Fenômenos Geológicos , Geologia , Origem da Vida , Erupções Vulcânicas
13.
Geochim Cosmochim Acta ; 61(7): 1359-412, 1997 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-11541435

RESUMO

A large number of aqueous metal complexes contribute significantly to hydrothermal, metamorphic, and magmatic processes in the crust of the Earth. Nevertheless, relatively few thermodynamic data other than dissociation constants (K) for a few dozen of these complexes have been determined experimentally at elevated temperatures and pressures. The calculations summarized below are intended to supplement these experimental data by providing interim predictions of the thermodynamic properties of supercritical aqueous metal complexes using the revised HKF (Helgeson et al., 1981) equations of state for aqueous species (Tanger and Helgeson, 1988; Shock et al., 1992) and correlations among equations of state parameters and standard partial molal properties at 25 degrees C and 1 bar (Shock and Helgeson, 1988, 1990; Shock et al., 1989). These equations and correlations permit retrieval of the conventional standard partial molal entropies (mean S0), volumes (mean V0), and heat capacities (mean C0P) of aqueous metal complexes at 25 degrees C and 1 bar from published values of log K in the supercritical region and the limited number of experimental dissociation constants available in the literature over relatively short ranges of elevated temperature at PSAT (PSAT and SAT are used in the present communication to refer to pressures corresponding to liquid-vapor equilibrium for the system H2O except at temperatures <100 degrees C, where they refer to the reference pressure of 1 bar). The standard partial molal properties computed in this way can then be used to generate corresponding values of delta mean S0, delta mean V0, and delta mean C0P of association, which for similar complexes correlate linearly with mean S0, mean V0 and mean C0P, respectively, of the constituent cations and ligands at 25 degrees C and 1 bar. Generalizing these correlations and combining them with the equations of state permits prediction of the temperature and pressure dependence of log K and other thermodynamic properties of a large number of aqueous metal complexes. As a consequence, it is possible to retrieve values of log K at 25 degrees C and 1 bar from the results of hydrothermal experiments at higher temperatures and pressures or to predict values of log K at hydrothermal conditions when no experimental data are available at temperatures and pressures above 25 degrees C and 1 bar. Such predictions can be made for temperatures and pressures from 0 degrees C and 1 bar to 1000 degrees C and 5000 bars.


Assuntos
Planeta Terra , Metais/química , Minerais/química , Modelos Químicos , Temperatura , Termodinâmica , Algoritmos , Pressão Atmosférica , Fenômenos Geológicos , Geologia , Temperatura Alta , Matemática
14.
J Geophys Res ; 102(E4): 9135-43, 1997 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-11541456

RESUMO

If hydrothermal Systems existed on Mars, hydration of crustal rocks may have had the potential to affect the water budget of the planet. We have conducted geochemical model calculations to investigate the relative roles of host rock composition, temperature, water-to-rock ratio, and initial fluid oxygen fugacity on the mineralogy of hydrothermal alteration assemblages, as well as the effectiveness of alteration to store water in the crust as hydrous minerals. In order to place calculations for Mars in perspective, models of hydrothermal alteration of three genetically related Icelandic volcanics (a basalt, andesite, and rhyolite) are presented, together with results for compositions based on SNC meteorite samples (Shergotty and Chassigny). Temperatures from 150 degrees C to 250 degrees C, water-to-rock ratios from 0.1 to 1000, and two initial fluid oxygen fugacities are considered in the models. Model results for water-to-rock ratios less than 10 are emphasized because they are likely to be more applicable to Mars. In accord with studies of low-grade alteration of terrestrial rocks, we find that the major controls on hydrous mineral production are host rock composition and temperature. Over the range of conditions considered, the alteration of Shergotty shows the greatest potential for storing water as hydrous minerals, and the alteration of Icelandic rhyolite has the lowest potential.


Assuntos
Evolução Planetária , Sedimentos Geológicos/análise , Marte , Modelos Químicos , Água , Exobiologia , Meio Ambiente Extraterreno , Fenômenos Geológicos , Geologia , Temperatura Alta , Radical Hidroxila , Islândia , Meteoroides , Minerais/análise , Silicatos/análise
15.
Geochim Cosmochim Acta ; 61(5): 907-50, 1997 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-11541225

RESUMO

Correlations among experimentally determined standard partial molal thermodynamic properties of inorganic aqueous species at 25 degrees C and 1 bar allow estimates of these properties for numerous monatomic cations and anions, polyatomic anions, oxyanions, acid oxyanions, neutral oxy-acid species, dissolved gases, and hydroxide complexes of metal cations. Combined with correlations among parameters in the revised Helgeson-Kirkham-Flowers (HKF) equation of state (Shock et al., 1992), these estimates permit predictions of standard partial molal volumes, heat capacities, and entropies, as well as apparent standard partial molal enthalpies and Gibbs free energies of formation to 1000 degrees C and 5 kb for hundreds of inorganic aqueous species of interest in geochemistry. Data and parameters for more than 300 inorganic aqueous species are presented. Close agreement between calculated and experimentally determined equilibrium constants for acid dissociation reactions and cation hydrolysis reactions supports the generality and validity of these predictive methods. These data facilitate the calculation of the speciation of major, minor, and trace elements in hydrothermal and metamorphic fluids throughout most of the crust of the Earth.


Assuntos
Geologia , Hidróxidos/química , Íons , Temperatura , Termodinâmica , Água/química , Algoritmos , Ânions/química , Pressão Atmosférica , Cátions/química , Eletrólitos , Fenômenos Geológicos , Matemática , Metais/química , Modelos Químicos , Oxigênio/química
16.
J Geophys Res ; 102(E10): 23687-94, 1997 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-11541237

RESUMO

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.


Assuntos
Evolução Química , Exobiologia , Temperatura Alta , Marte , Microbiologia da Água , Euryarchaeota , Água Doce/química , Água Doce/microbiologia , Sedimentos Geológicos/química , Sedimentos Geológicos/microbiologia , Fenômenos Geológicos , Geologia , Água do Mar/química , Água do Mar/microbiologia , Termodinâmica
17.
Geochim Cosmochim Acta ; 61(20): 4375-91, 1997 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-11541662

RESUMO

Mixing of hydrothermal fluids and seawater at the ocean floor, combined with slow reaction kinetics for oxidation/reduction reactions, provides a source of metabolic energy for chemolithotrophic microorganisms which are the primary biomass producers for an extensive submarine ecosystem that is essentially independent of photosynthesis. Thermodynamic models are used to explore geochemical constraints on the amount of metabolic energy potentially available from chemosynthetic reactions involving S, C, Fe, and Mn compounds during mixing of hydrothermal fluids with seawater. For the vent fluid used in the calculations (EPR 21 degrees N OBS), the model indicates that mixing environments are favorable for oxidation of H2S, CH4, Fe2+ and Mn2+ only below approximately 38 degrees C, with methanogenesis and reduction of sulfate or S degrees favored at higher temperatures, suggesting that environments dominated by mixing provide habitats for mesophilic (but not thermophilic) aerobes and thermophilic (but not mesophilic) anaerobes. A maximum of approximately 760 cal per kilogram vent fluid is available from sulfide oxidation while between 8 and 35 cal/kg vent fluid is available from methanotrophy, methanogenesis, oxidation of Fe or Mn, or sulfate reduction. The total potential for chemosynthetic primary production at deep-sea hydrothermal vents globally is estimated to be about 10(13) g biomass per year, which represents approximately 0.02% of the global primary production by photosynthesis in the oceans. Thermophilic methanogens and sulfate- and S degree-reducers are likely to be the predominant organisms in the walls of vent chimneys and in the diffuse mixing zones beneath warm vents, where biological processes may contribute to the high methane concentrations of vent fluids and heavy 34S/32S ratios of vent sulfide minerals. The metabolic processes taking place in these systems may be analogs of the first living systems to evolve on the Earth.


Assuntos
Biomassa , Temperatura Alta , Água do Mar/química , Água do Mar/microbiologia , Enxofre/metabolismo , Aerobiose , Anaerobiose , Carbono/química , Carbono/metabolismo , Ecossistema , Euryarchaeota/metabolismo , Fenômenos Geológicos , Geologia , Sulfeto de Hidrogênio/química , Ferro/metabolismo , Manganês/química , Manganês/metabolismo , Metano/metabolismo , Modelos Químicos , Oxirredução , Sulfatos/química , Sulfatos/metabolismo , Enxofre/química , Bactérias Redutoras de Enxofre/metabolismo , Temperatura , Termodinâmica , Microbiologia da Água
18.
Ciba Found Symp ; 202: 40-52; discussion 52-60, 1996.
Artigo em Inglês | MEDLINE | ID: mdl-9243009

RESUMO

Analysis of the chemical disequilibrium provided by the mixing of hydrothermal fluids and seawater in present-day systems indicates that organic synthesis from CO2 or carbonic acid is thermodynamically favoured in the conditions in which hyperthermophilic microorganisms are known to live. These organisms lower the Gibbs free energy of the chemical mixture by synthesizing many of the components of their cells. Primary productivity is enormous in hydrothermal systems because it depends only on catalysis of thermodynamically favourable, exergonic reactions. It follows that hydrothermal systems may be the most favourable environments for life on Earth. This fact makes hydrothermal systems logical candidates for the location of the emergence of life, a speculation that is supported by genetic evidence that modern hyperthermophilic organisms are closer to a common ancestor than any other forms of life. The presence of hydrothermal systems on the early Earth would correspond to the presence of liquid water. Evidence that hydrothermal systems existed early in the history of Mars raises the possibility that life may have emerged on Mars as well. Redox reactions between water and rock establish the potential for organic synthesis in and around hydrothermal systems. Therefore, the single most important parameter for modelling the geochemical emergence of life on the early Earth or Mars is the composition of the rock which hosts the hydrothermal system.


Assuntos
Planeta Terra , Meio Ambiente , Temperatura Alta , Marte , Carbono/química , Dióxido de Carbono/química , Química Orgânica , Metabolismo Energético , Meio Ambiente Extraterreno , Sedimentos Geológicos/microbiologia , Fenômenos Geológicos , Geologia , Concentração de Íons de Hidrogênio , Metano/química , Minerais/metabolismo , Modelos Biológicos , Fenômenos de Química Orgânica , Oxirredução , Água do Mar/química , Água do Mar/microbiologia , Termodinâmica , Microbiologia da Água
19.
Nature ; 378(6555): 338-9, 1995 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-11536708

RESUMO

NASA: The author examines conflicting models, especially evidence from Price and Schoell in this issue (see comment), for the creation of ore deposits and the movement of petroleum. The Bakken formation in North Dakota is used as an example of a petroleum reservoir that has not migrated from its original site. Analysis of natural gases at the site indicates a difference in gas distribution between the Bakken site and migratory sites. Controversies are examined in the context of advances in fluid-flow calculations and high-temperature methanogenic reactions.^ieng


Assuntos
Gases/análise , Metano/química , Euryarchaeota , Combustíveis Fósseis , Fenômenos Geológicos , Geologia , Metano/síntese química , Metano/metabolismo , North Dakota
20.
Nature ; 377(6548): 406-8, 1995 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-7566116

RESUMO

It is often argued that substantially more carbon dioxide and water were degassed from the martian interior than can be found at present in the atmosphere, polar caps and regolith. Calculations have shown that atmospheric escape cannot account for all of the missing volatiles. Suggestions that carbon dioxide is stored as marine or lacustrine deposits, are challenged by Earth-based and spacecraft remote-sensing data. Moreover, recent modelling of the martian atmosphere suggests that rainfall or open bodies of water are in any case unlikely to have persisted for extended periods of time. Hydrothermal carbonates therefore provide a possible solution to this dilemma. Using an accessible terrestrial system (Iceland) as a guide to the underlying processes, and a host rock composition inferred from the least-altered martian meteorite, we present a geochemical model for the formation of carbonates in possible martian hydrothermal systems. Our results suggest that an extensive reservoir of carbonate minerals--equivalent to an atmospheric pressure of carbon dioxide of at least one bar--could have been sequestered beneath the surface by widespread hydrothermal activity in the martian past.


Assuntos
Carbonatos/análise , Meio Ambiente Extraterreno , Marte , Dióxido de Carbono/química , Carbonatos/química , Fenômenos Geológicos , Geologia , Islândia , Modelos Químicos , Temperatura , Água/química
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