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PubMed1990

The C7 cluster: structure and infrared frequencies.

Observation and characterization of the C7 cluster are reported. Carbon clusters are produced by laser vaporization of a graphite target followed by supersonic expansion of the vaporized material within a gas dynamically focused argon jet. Thirty-six sequential rovibrational lines of the nu 4 antisymmetric stretch fundamental of C7 are probed by gated detection of diode laser absorption. The observed spectrum is characteristic of a symmetrical linear molecule. Analysis of the spectrum indicates an effective average bond length of 1.2736(4) angstroms and a vibrational frequency of 2138.1951(10) reciprocal centimeters, in excellent agreement with ab initio calculations. This work will facilitate the astrophysical detection of this cluster.

Argon↗
PubMed1990

Tunable far-IR laser spectroscopy of jet-cooled carbon clusters: the nu 2 bending vibration of C3.

Seven rovibrational transitions of the (01(1)0) <-- (00(0)0) fundamental bending band of C3 have been measured with high precision with the use of a tunable far-infrared laser spectrometer. The C3 molecules were produced by laser vaporization of a graphite rod and cooled in a supersonic expansion. The astrophysically important nu 2 fundamental frequency is determined to be 63.416529(40) cm-1. These measurements provide the basis for studies of C3 in the interstellar medium with far-infrared astronomy.

Astronomy↗
PubMed1991

Aerobic sulfate reduction in microbial mats.

Measurements of bacterial sulfate reduction and dissolved oxygen (O2) in hypersaline bacterial mats from Baja California, Mexico, revealed that sulfate reduction occurred consistently within the well-oxygenated photosynthetic zone of the mats. This evidence that dissimilatory sulfate reduction can occur in the presence of O2 challenges the conventional view that sulfate reduction is a strictly anaerobic process. At constant temperature, the rates of sulfate reduction in oxygenated mats during daytime were similar to rates in anoxic mats at night: thus, during a 24-hour cycle, variations in light and O2 have little effect on rates of sulfate reduction in these mats.

Bacteria, Aerobic↗
PubMed1991

The greenhouse and antigreenhouse effects on Titan.

There are many parallels between the atmospheric thermal structure of the Saturnian satellite Titan and the terrestrial greenhouse effect; these parallels provide a comparison for theories of the heat balance of Earth. Titan's atmosphere has a greenhouse effect caused primarily by pressure-induced opacity of N2, CH4, and H2. H2 is a key absorber because it is primarily responsible for the absorption in the wave number 400 to 600 cm-1 "window" region of Titan's infrared spectrum. The concentration of CH4, also an important absorber, is set by the saturation vapor pressure and hence is dependent on temperature. In this respect there is a similarity between the role of H2 and CH4 on Titan and that of CO2 and H2O on Earth. Titan also has an antigreenhouse effect that results from the presence of a high-altitude haze layer that is absorbing at solar wavelengths but transparent in the thermal infrared. The antigreenhouse effect on Titan reduces the surface temperature by 9 K whereas the greenhouse effect increases it by 21 K. The net effect is that the surface temperature (94 K) is 12 K warmer than the effective temperature (82 K). If the haze layer were removed, the antigreenhouse effect would be greatly reduced, the greenhouse effect would become even stronger, and the surface temperature would rise by over 20 K.

Atmosphere↗
PubMed1991

The dark side of Venus: near-infrared images and spectra from the Anglo-Australian observatory.

Near-infrared images and spectra of the night side of Venus taken at the Anglo-Australian Telescope during February 1990 reveal four new thermal emission windows at 1.10, 1.18, 1.27, and 1.31 micrometers, in addition to the previously discovered windows at 1.74 and 2.3 micrometers. Images of the Venus night side show similar bright and dark markings in all windows, but their contrast is much lower at short wavelengths. The 1.27-micrometers window includes a bright, high-altitude O2 airglow feature in addition to a thermal contribution from the deep atmosphere. Simulations of the 1.27- and 2.3 micrometers spectra indicate water vapor mixing ratios near 40 +/- 20 parts per million by volume between the surface and the cloud base. No large horizontal gradients in the water vapor mixing ratios were detected at these altitudes.

Astronomy↗
PubMed1994

Structural transitions in amorphous water ice and astrophysical implications.

Selected area electron diffraction is used to monitor structural changes of vapor-deposited water ice in vacuum during warm-up from 15 to 188 K. A progression of three amorphous forms of water ice is found with well-defined transitions. The formation of a high-density amorphous form (Iah) at 15 K is confirmed, and the transition to the more familiar low-density form (Ial) occurs gradually over the range 38 to 68 K. At 131 K, the ice transforms into a third amorphous form (Iar), which precedes the crystallization of cubic ice (Ic) and coexists metastably with Ic from 148 K until at least 188 K. These structural transformations of amorphous water ice can be used to explain hitherto anomalous properties of astrophysical ices. The structural transition from Iah to Ial is responsible for the diffusion and recombination of radicals in ultraviolet-photolyzed interstellar ices at low temperatures. The occurrence and persistence of Iar explains anomalous gas retention and gas release from water-rich ices at temperatures above 150 K.

Algorithms↗
PubMed1986

Climatic consequences of very high carbon dioxide levels in the earth's early atmosphere.

The possible consequences of very high carbon dioxide concentrations in the earth's early atmosphere have been investigated with a radiative-convective climate model. The early atmosphere would apparently have been stable against the onset of a runaway greenhouse (that is, the complete evaporation of the oceans) for carbon dioxide pressures up to at least 100 bars. A 10- to 20-bar carbon dioxide atmosphere, such as may have existed during the first several hundred million years of the earth's history, would have had a surface temperature of approximately 85 degrees to 110 degrees C. The early stratosphere should have been dry, thereby precluding the possibility of an oxygenic prebiotic atmosphere caused by photodissociation of water vapor followed by escape of hydrogen to space. Earth's present atmosphere also appears to be stable against a carbon dioxide-induced runaway greenhouse.

Atmosphere↗
PubMed1987

Natural abundances of carbon isotopes in acetate from a coastal marine sediment.

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

Acetates↗
PubMed1989

Diode-laser absorption spectroscopy of supersonic carbon cluster beams: the nu 3 spectrum of C5.

A new spectroscopic experiment has been developed in which rovibrational transitions of supersonically cooled carbon clusters, which were produced by laser vaporization of graphite, have been measured by direct-absorption diode-laser spectroscopy. Thirty-six sequential rovibrational lines of the nu 3 band of the C5 carbon cluster have been measured with Doppler-limited resolution. The absorption spectrum is characteristic of a linear molecule with a center of symmetry. Least-squares analysis of the spectrum indicates an effective carbon-carbon bond length of 1.283 angstroms, in good agreement with ab initio quantum chemical calculations. This work confirms the detection of C5 in IRC + 10216 reported in the accompanying paper.

Astronomical Phenomena↗
PubMed1996

Search for past life on Mars: possible relic biogenic activity in martian meteorite ALH84001.

Fresh fracture surfaces of the martian meteorite ALH84001 contain abundant polycyclic aromatic hydrocarbons (PAHs). These fresh fracture surfaces also display carbonate globules. Contamination studies suggest that the PAHs are indigenous to the meteorite. High-resolution scanning and transmission electron microscopy study of surface textures and internal structures of selected carbonate globules show that the globules contain fine-grained, secondary phases of single-domain magnetite and Fe-sulfides. The carbonate globules are similar in texture and size to some terrestrial bacterially induced carbonate precipitates. Although inorganic formation is possible, formation of the globules by biogenic processes could explain many of the observed features, including the PAHs. The PAHs, the carbonate globules, and their associated secondary mineral phases and textures could thus be fossil remains of a past martian biota.

Antarctic Regions↗
PubMed1997

Low-temperature carbonate concretions in the Martian meteorite ALH84001: evidence from stable isotopes and mineralogy.

The martian meteorite ALH84001 contains small, disk-shaped concretions of carbonate with concentric chemical and mineralogical zonation. Oxygen isotope compositions of these concretions, measured by ion microprobe, range from delta18O = +9.5 to +20.5 per thousand. Most of the core of one concretion is homogeneous (16.7 +/- 1.2 per thousand) and over 5 per thousand higher in delta18O than a second concretion. Orthopyroxene that hosts the secondary carbonates is isotopically homogeneous (delta18O = 4.6 +/- 1.2 per thousand). Secondary SiO2 has delta18O = 20.4 per thousand. Carbon isotope ratios measured from the core of one concretion average delta13C = 46 +/- 8 per thousand, consistent with formation on Mars. The isotopic variations and mineral compositions offer no evidence for high temperature (>650 degrees C) carbonate precipitation and suggest non-equilibrium processes at low temperatures (< approximately 300 degrees C).

Carbon Isotopes↗
PubMed1997

Organic synthesis in experimental impact shocks.

Laboratory simulations of shocks created with a high-energy laser demonstrate that the efficacy of organic production depends on the molecular, not just the elemental composition of the shocked gas. In a methane-rich mixture that simulates a low-temperature equilibrium mixture of cometary material, hydrogen cyanide and acetylene were produced with yields of 5 x 10(17) molecules per joule. Repeated shocking of the methane-rich mixture produced amine groups, suggesting the possible synthesis of amino acids. No organic molecules were produced in a carbon dioxide-rich mixture, which is at odds with thermodynamic equilibrium approaches to shock chemistry and has implications for the modeling of shock-produced organic molecules on early Earth.

Acetylene↗
PubMed1995

Collision of comet Shoemaker-Levy 9 with Jupiter observed by the NASA infrared telescope facility.

The National Aeronautics and Space Administration (NASA) Infrared Telescope Facility was used to investigate the collision of comet Shoemaker-Levy 9 with Jupiter from 12 July to 7 August 1994. Strong thermal infrared emission lasting several minutes was observed after the impacts of fragments C, G, and R. All impacts warmed the stratosphere and some the troposphere up to several degrees. The abundance of stratospheric ammonia increased by more than 50 times. Impact-related particles extended up to a level where the atmospheric pressure measured several millibars. The north polar near-infrared aurora brightened by nearly a factor of 5 a week after the impacts.

Ammonia↗
PubMed1995

Identification of methanotrophic lipid biomarkers in cold-seep mussel gills: chemical and isotopic analysis.

A lipid analysis of the tissues of a cold-seep mytilid mussel collected from the Louisiana slope of the Gulf of Mexico was used in conjunction with a compound-specific isotope analysis to demonstrate the presence of methanotrophic symbionts in the mussel gill tissue and to demonstrate the host's dependence on bacterially synthesized metabolic intermediates. The gill tissue contained large amounts of group-specific methanotrophic biomarkers, bacteriohopanoids, 4-methylsterols, lipopolysaccharide-associated hydroxy fatty acids, and type I-specific 16:1 fatty acid isomers with bond positions at delta 8, delta 10, and delta 11. Only small amounts of these compounds were detected in the mantle or other tissues of the host animal. A variety of cholesterol and 4-methylsterol isomers were identified as both free and steryl esters, and the sterol double bond positions suggested that the major bacterially derived gill sterol [11.0% 4 alpha-methyl-cholesta-8(14),24-dien-3 beta-ol] was converted to host cholesterol (64.2% of the gill sterol was cholest-5-en-3 beta-ol). The stable carbon isotope values for gill and mantle preparations were, respectively, -59.0 and -60.4% for total tissue, -60.6 and -62.4% for total lipids, -60.2 and-63.9% for phospholipid fatty acids, and -71.8 and 73.8% for sterols. These stable carbon isotope values revealed that the relative fractionation pattern was similar to the patterns obtained in pure culture experiments with methanotrophic bacteria (R.E. Summons, L.L. Jahnke, and Z. Roksandic, Geochim. Cosmochim. Acta 58: 2853-2863, 1994) further supporting the conversion of the bacteria methylsterol pool.

Alkanes↗
PubMed1990

DNA dynamics in aqueous solution: opening the double helix.

The opening of a DNA base pair is a simple reaction that is a prerequisite for replication, transcription, and other vital biological functions. Understanding the molecular mechanisms of biological reactions is crucial for predicting and, ultimately, controlling them. Realistic computer simulations of the reactions can provide the needed understanding. To model even the simplest reaction in aqueous solution requires hundreds of hours of supercomputing time. We have used molecular dynamics techniques to simulate fraying of the ends of a six base pair double strand of DNA, [TCGCGA]2, where the four bases of DNA are denoted by T (thymine), C (cytosine), G (guanine), and A (adenine), and to estimate the free energy barrier to this process. The calculations, in which the DNA was surrounded by 2,594 water molecules, required 50 hours of CRAY-2 CPU time for every simulated 100 picoseconds. A free energy barrier to fraying, which is mainly characterized by the movement of adenine away from thymine into aqueous environment, was estimated to be 4 kcal/mol. Another fraying pathway, which leads to stacking between terminal adenine and thymine, was also observed. These detailed pictures of the motions and energetics of DNA base pair opening in water are a first step toward understanding how DNA will interact with any molecule.

Adenine↗
PubMed1991

Highly mobile oxygen hole-type charge carriers in fused silica.

Some peculiar positive charge carriers are thermally generated in fused silica above 500 degrees C. These charge carriers appear to be positive holes, chemically O- states, probably arising from dissociation of peroxy defects. The charge carriers give rise to a pronounced positive surface charge which disappears upon cooling but can be quenched by rapid quenching from approximately 800 degrees C. Reheating to approximately 200 degrees C remobilizes these charge carriers and causes them to anneal below 400 degrees C. The generation of positive holes charge carriers may be important to understand failure mechanisms of SiO2 insulators.

Electric Conductivity↗
PubMed1991

Sulfate reduction in deep-sea sediments.

Sulfate reduction rates calculated from about 200 DSDP pore water sulfate profiles have been contoured and plotted on a map covering most areas of the world ocean. Rates show a remarkable spatial consistency, with high rates observed near the continental margins, becoming progressively lower toward the central ocean basins. Relatively elevated rates are also found in the eastern equatorial Pacific, a site of upwelling and correspondingly high rates of primary organic production. Overall, the distribution of sulfate reduction in pelagic sediments looks very similar to the distribution of primary organic carbon production. When rates are directly compared, however, the correlation between sulfate reduction and primary production is only moderately strong. Perhaps the most important influence on sulfate reduction is sediment deposition rate and the control this has over the fraction of the sedimentary organic carbon flux that becomes available for sulfate reduction. The slower the rate of sediment deposition the more time for oxic respiration and the less organic carbon that escapes to the zone of sulfate reduction. To predict most accurately sulfate reduction rates, however, the variables of primary production, water depth, and sediment deposition rate must all be integrated.

Algorithms↗
PubMed1988

Optical properties of benthic photosynthetic communities: fiber-optic studies of cyanobacterial mats.

A fiber-optic microphobe was used to analyze the spectral light gradients in benthic cyanobacterial mats with 50-micrometer depth resolution and 10-nm spectral resolution. Microcoleus chthononplastes mats were collected from hypersaline, coastal ponds at Guerrero Negro, Baja California. Gradients of spectral radiance, L, were measured at different angles through the mats and the spherically integrated scalar irradiance, Eo, was calculated. Maximal spectral light attenuation was found at the absorption peaks for the dominant photosynthetic pigments: chlorophyll a at 430 and 670 nm, carotenoids at 450-500 nm, phycocyanin at 620 nm, and bacteriochlorophyll a at 800-900 nm. Scattered light had a marked spectral effect on the scalar irradiance which near the mat surface reached up to 190% of the incident irradiance. The spherically integrated irradiance thus differed strongly from the incident irradiance both in total intensity and in spectral composition. These basic optical properties are important for the understanding of photosynthesis and light harvesting in benthic and epiphytic communities.

Bacteriochlorophylls↗