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Long-term productivity in the cryptoendolithic microbial community of the Ross Desert, Antarctica.

Annual gross productivity of the lichen-dominated cryptoendolithic community was calculated from a computer analysis of photosynthetic response based on laboratory measurements of CO2 exchange and three years (1985-1988) of field nanoclimate data. Photosynthetic optimum increased from -3 to 2 degrees C between irradiance levels of 100 and 1500 micromoles photons m-2 s-1, while the upper compensation point rose from 1 to 17 degrees C. The mean yearly total time available for metabolic activity (temperature above -10 degrees C and moisture present) was 771.3 h for horizontal rock, 421.5 h for northeast-oriented sloped rock, and 1042.2 h for a small depression in horizontal rock (the characteristic site of occasional lichen apothecia). The calculated mean gross productivity value for a horizontal rock was 1215 mg C m-2 y-1, and net photosynthetic gain was 606 mg C m-2 y-1. Net ecosystem productivity (annual accretion of cellular biomass) estimated from long-term events amounted to only about 3 mg C m-2 y-1. The difference between these two values may represent the long-term metabolic costs of the frequent dehydration-rehydration and freezing-thawing cycles or of overwintering, and may account for the leaching of organic substances to the rock. The yearly gross productivity of the cryptoendolithic microbial community of the entire Ross Desert area was estimated at approximately 120,000-180,000 kg C. Of this, 600-900 kg C is in microbial biomass, and much of the rest is soluble compounds that leach into the rocks and possibly percolate to the valleys, providing a source of organic matter for lakes, rivers, and soils.

Antarctic Regions↗

Mobilifilum chasei: morphology and ecology of a spirochete from an intertidal stratified microbial mat community.

Spirochetes were found in the lower anoxiphototrophic layer of a stratified microbial mat (North Pond, Laguna Figueroa, Baja California, Mexico). Ultra-structural analysis of thin sections of field samples revealed spirochetes approximately 0.25 micrometer in diameter with 10 or more periplasmic flagella, leading to the interpretation that these spirochetes bear 10 flagellar insertions on each end. Morphometric study showed these free-living spirochetes greatly resemble certain symbiotic ones, i.e., Borrelia and certain termite spirochetes, the transverse sections of which are presented here. The ultrastructure of this spirochete also resembles Hollandina and Diplocalyx (spirochetes symbiotic in arthropods) more than it does Spirochaeta, the well known genus of mud-dwelling spirochetes. The new spirochete was detected in mat material collected both in 1985 and in 1987. Unique morphology (i.e., conspicuous outer coat of inner membrane, large number of periplasmic flagella) and ecology prompt us to name a new free-living spirochete.

Animals↗

Characterization of 15 selected coccal bacteria isolated from Antarctic rock and soil samples from the McMurdo-Dry Valleys (South-Victoria Land).

Approximately 1500 cultures of microorganisms were isolated from rocks and soils of the Ross Desert (McMurdo-Dry Valleys). From these, 15 coccoid strains were chosen for more detailed investigation. They were characterized by morphological, physiological and chemotaxonomical properties. All isolates were Gram-positive, catalase-positive and nonmotile. Six strains showed red pigmentation and could be identified as members of the genera Micrococcus (M. roseus, M. agilis) or Deinococcus. In spite of their coccoid morphology, the remaining nine strains had to be associated with coryneform bacteria (Arthrobacter, Brevibacterium), because of their cell wall composition and G+C ratios. Most of the strains were psychrotrophic, but one strain was even obligately psychrophilic, with a temperature maximum below 20 degrees C. Red cocci had in vitro pH optima above 9.0 although they generally originated from acid samples. Most isolates showed a preference for sugar alcohols and organic acids, compounds which are commonly known to be released by lichens, molds and algae, the other components of the cryptoendolithic ecosystem. These properties indicate that our strains are autochthonous members of the natural Antarctic microbial population.

Antarctic Regions↗

The cryptoendolithic microbial environment in the Ross Desert of Antarctica: satellite-transmitted continuous nanoclimate data, 1984 to 1986.

A satellite mediated station for monitoring nanoclimate (climate in the millimeter range) data, suitable for use in polar regions is described. The station, located in the Ross desert of Antarctica, has been in operation for more than 3 years, measuring rock temperatures, air temperature, light, snow, wind, and moisture. The data indicate that biological activity in the cryptoendolithic microbial ecosystem is limited to the period from mid November to mid February. The total number of hours of biological activity, based on assumptions of the minimum light, temperature and moisture requirements of the community, is less than 1000 h/year. The time above 0 degrees C, representing more nearly optimal conditions, is between 50 and 550 h/year, depending on the orientation of the surface.

Antarctic Regions↗

Photochemical fractionation of 16O in the space medium modeled by resonance excitation of CO by H-Lyman alpha.

Inferences about the formation of primordial matter in our solar system rest on analysis of the earliest preserved materials in meteorites, of the structure of the solar system today, and of matter in evolving stellar systems elsewhere. The isotope distribution in meteorites suggests that molecular excitation processes similar to those observed today in circumstellar regions and dark interstellar clouds were operating in the early solar nebula. Laboratory model experiments together with these observations give evidence on the thermal state of the source medium from which refractory meteoritic dust formed. They indicate that resonance excitation of the broad isotopic bands of molecules such as 12C16O, MgO, O2, AlO, and OH by strong UV line sources such as H-L alpha, Mg II, H beta, and Ca II may induce selective reactions resulting in the anomalous isotopic composition of oxygen and possibly other elements in refractory oxide condensates in meteorites.

Carbon↗

Upper limits for the ethyl-cyanide abundances in TMC-1 and L134N: chemical implications.

We have sought interstellar ethyl-cyanide via its 2(02)-1(01) transition towards two cold, dark clouds and report upper limits of the total column densities of 3 x 10(12) cm-2 and 2 x 10(12) cm-2 for TMC-1 and L134N, respectively. We also observed the 2(02)-1(01) transition of vinyl cyanide previously identified in TMC-1 by Matthews and Sears (1983b). The detection of vinyl cyanide and the non-detection of ethyl cyanide in TMC-1 are consistent with gas phase ion-molecule chemical models, and there is thus no necessity of invoking grain surface synthesis for vinyl cyanide in cold clouds.

Acrylonitrile↗

Observations of chemical processing in the circumstellar environment.

High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NCG 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.

Astronomical Phenomena↗

Chemical evolution of circumstellar matter around young stellar objects.

Recent observational studies of the chemical composition of circumstellar matter around both high- and low-mass young stellar objects are reviewed. The molecular abundances are found to be a strong function of evolutionary state, but not of system mass or luminosity. The data are discussed with reference to recent theoretical models.

Astronomical Phenomena↗

An algorithm for converting a virtual-bond chain into a complete polypeptide backbone chain.

A systematic analysis is presented of the algorithm for converting a virtual-bond chain, defined by the coordinates of the alpha-carbons of a given protein, into a complete polypeptide backbone. An alternative algorithm, based upon the same set of geometric parameters used in the Purisima-Scheraga algorithm but with a different "linkage map" of the algorithmic procedures, is proposed. The global virtual-bond chain geometric constraints are more easily separable from the loal peptide geometric and energetic constraints derived from, for example, the Ramachandran criterion, within the framework of this approach.

Algorithms↗

Evidence for organic synthesis in high temperature aqueous media--facts and prognosis.

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to >400 degrees C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS kappa- in the hydrothermal fluids. Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200-350 degrees C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 degrees C.

Amino Acids↗

Geochemical constraints on chemolithoautotrophic reactions in hydrothermal systems.

Thermodynamic calculations provide the means to quantify the chemical disequilibrium inherent in the mixing of reduced hydrothermal fluids with seawater. The chemical energy available for metabolic processes in these environments can be evaluated by taking into account the pressure and temperature dependence of the apparent standard Gibbs free energies of reactions in the S-H2-H2O system together with geochemical constraints on pH, activities of aqueous sulfur species and fugacities of H2 and/or O2. Using present-day mixing of hydrothermal fluids and seawater as a starting point, it is shown that each mole of H2S entering seawater from hydrothermal fluids represents about 200,000 calories of chemical energy for metabolic systems able to catalyze H2S oxidation. Extrapolating to the early Earth, which was likely to have had an atmosphere more reduced than at present, shows that this chemical energy may have been a factor of two or so less. Nevertheless, mixing of hydrothermal fluids with seawater would have been an abundant source of chemical energy, and an inevitable consequence of the presence of an ocean on an initially hot Earth. The amount of energy available was more than enough for organic synthesis from CO2 or CO, and/or polymer formation, indicating that the vicinity of hydrothermal systems at the sea floor was an ideal location for the emergence of the first chemolithoautotrophic metabolic systems.

Archaea↗

Thermodynamics of Strecker synthesis in hydrothermal systems.

Submarine hydrothermal systems on the early Earth may have been the sites from which life emerged. The potential for Strecker synthesis to produce biomolecules (amino and hydroxy acids) from starting compounds (ketones, aldehydes, HCN and ammonia) in such environments is evaluated quantitatively using thermodynamic data and parameters for the revised Helgeson-Kirkham-Flowers (HKF) equation of state. Although there is an overwhelming thermodynamic drive to form biomolecules by the Strecker synthesis at hydrothermal conditions, the availability and concentration of starting compounds limit the efficiency and productivity of Strecker reactions. Mechanisms for concentrating reactant compounds could help overcome this problem, but other mechanisms for production of biomolecules may have been required to produce the required compounds on the early Earth. Geochemical constraints imposed by hydrothermal systems provide important clues for determining the potential of these and other systems as sites for the emergence of life.

Aldehydes↗

The binding and reactions of nucleotides and polynucleotides on iron oxide hydroxide polymorphs.

The iron oxide hydroxide minerals goethite and akaganéite were likely constituents of the sediments present in, for instance, geothermal regions of the primitive earth. They may have adsorbed organics and catalyzed the condensation processes which led to the origins of life. The binding to and reactions of nucleotides and oligonucleotides with these minerals was investigated. The adsorption of adenosine, 5'-AMP, 3'-AMP, 5'-UMP, and 5'-CMP to these minerals was studied. Adenosine did not bind to goethite and akaganéite. The adsorption isotherms for the binding of the nucleotides revealed that they all had close to the same affinity for the mineral. Binding to goethite was about four times stronger than to akaganéite. There was little difference in the adsorption of each nucleotide suggesting the binding was between the negative charge on the phosphate group and the positive charges on the mineral surface. The absence of binding of adenosine is consistent with this explanation. Binding decreases as the pH increases due to the titration of the positive (acidic) centers on the minerals. Two times as many moles of polynucleotides were bound to these minerals as compared to the mononucleotides. Watson-Crick hydrogen bonding of adenosine and 5'-AMP to poly(U) complexes with goethite and akaganéite was observed. There was no interaction of uridine with the poly(U)-goethite complex as expected if Watson-Crick hydrogen bonding is taking place. Neither goethite nor akaganéite catalyzed the oligomerization of the phosphorimidazolide of adenosine (ImpA). The template directed synthesis of oligomers of 5'-GMP on the poly(C) bound to goethite was observed. Higher molecular weight oligomers were observed when the poly(C) was bound to goethite than was found in the absence of the mineral.

Adenosine↗

Confined-pyrolysis as an experimental method for hydrothermal organic synthesis.

A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic compounds and competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

Alkanes↗

Laboratory investigations of Mars: chemical and spectroscopic characteristics of a suite of clays as Mars soil analogs.

Two major questions have been raised by prior explorations of Mars. Has there ever been abundant water on Mars? Why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface? The work reported here describes a model soil system of Mars Soil Analog Materials, MarSAM, with attributes which could help resolve both of these dilemmas. The first set of MarSAM consisted of a suite of variably iron/calcium-exchanged montmorillonite clays. Several properties, including chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, of these clays have been examined. Also, simulations of the Viking Labeled Release Experiment using the MarSAM were performed. The results of these studies show that surface iron and adsorbed water are important determinants of clay behavior as evidenced by changes in reflectance, water absorption, and clay surface reactions. Thus, these materials provide a model soil system which reasonably satisfies the constraints imposed by the Viking analyses and remote spectral observations of the Martian surface, and which offers a sink for significant amounts of water. Finally, our initial results may provide insights into the mechanisms of reactions that occur on clay surfaces as well as a more specific approach to determining the mineralogy of Martian soils.

Aluminum Silicates↗

Aqueous organic geochemistry at high temperature/high pressure.

It is the purpose of this chapter to provide a description of the fate and chemical alterations of organic matter under hydrothermal conditions, with a brief overview of the geographic localities where these processes have been studied to date. Two major but overlapping aspects will be considered: (a) Alteration and degradation processes and reactions, both reductive and oxidative, and (b) synthesis processes and reactions that are primarily reductive.

Atmospheric Pressure↗