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At least 343 records · Page 19

The history of an atmosphere of impact origin

Most of the masses accreting onto the earth and terrestrial planets impacted at sufficiently high velocities to release their volatiles into the atmosphere by impact-heating. However, based on models of planetary growth by accumulation from solid bodies, the time-scale for accretion was sufficiently long that the average surface temperatures could not have risen above 320 K. Using measured reaction rates, the released volatiles should have been re-incorporated into the planet by hydrating the surface minerals and were subsequently buried during accretion. Rapid hydration of impact products precludes the formation of a thick atmosphere as the planet accreted. Thus, only the subsequent differentiation and evolution of the terrestrial planets determined the size and composition of each planet's atmosphere.

Jakosky, B. M.↗

Coupling Between Metabolism and Compartmentalization: Vesicle Growth in the Presence of Dipeptides

A fundamental unresolved question in studies on the origin of life is: how different, ubiquitous protocellular functions begun to work in concert setting the stage for Darwinian evolution of nascent life? From this perspective, of particular significance is coupling between growth of protocellular compartments and the encapsulated, primordial metabolism, which is one of the focal topics of the current ISSOL meeting. Specifically, growth and division of cells facilitated by the products of a metabolic reaction would confer an evolutionary advantage on protocells encapsulating this reaction, as their population would increase at the expense of other protocells. Along these lines, Adamala and Szostak have recently demonstrated that a dipeptide captured inside fatty acid vesicles catalyzes the formation of other dipeptides from activated monomers. Some of the newly synthesized dipeptides, in turn, are capable to promote competitive growth of vesicles in the presence of fatty acid micelles. As vesicles become larger, they adapt filamentous shape, which has been shown to promote their division. On the basis of computer simulations, we provide a molecularly detailed explanation of this process and draw conclusions about its generality.

Wei, C.↗

Meteorites, Organics and Fischer-Tropsch Type Reaction: Production and Destruction

There has been an ongoing debate about the relative importance about the various chemical reactions that fonned organics in the early solar system. One proposed method that has long been recognized as a potential source of organics is Fischer-Tropsch type (FTT) synthesis. This process is commonly used in industry to produce fuels (i.e., complex hydrocarbons) by catalytic hydrogenation of carbon monoxide. Hill and Nuth were the first to publish results of FTT experiments that also included Haber-Bosch (HB) processes (hydrogenation of nitrogen. Their findings included the production of nitrilebearing compounds as well as trace amounts of methyl amine. Previous experience with these reactions revealed that the organic coating deposited on the grains is also an efficient catalyst and that the coating is composed of insoluble organic matter (10M) and could be reminiscent of the organic matrix found in some meteorites. This current set of FTT-styled experiments tracks the evolution of a set of organics, amino acids, in detail.

Johnson, Natasha M.↗

Atmosphere revitalization for manned spacecraft - An assessment of technology readiness

The level of proficiency attained by the most effective physical and chemical regenerative processes capable of providing a habitable atmospheric environment in a spacecraft is assessed. It is shown that both the Sabatier and Bosh reactions are in a mature stage of technological readiness and can effectively reduce the carbon dioxide in a spacecraft. An electrochemical method for concentrating CO2 from an air environment offers promise to approach low levels of pCO2 control. Technological advances in the fields of solid polymer electrolytes and oxygen evolution electrocatalysts have led to a water electrolysis system that can maintain efficient performance for several years. Nitrogen supply and control of the composition of the spacecraft atmosphere is effectively provided by the circulating electrolyte technique.

Samonski, F. H., Jr.↗

Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

Tseng, S.-S.↗

Archaebacterial rhodopsin sequences: Implications for evolution

It was proposed over 10 years ago that the archaebacteria represent a separate kingdom which diverged very early from the eubacteria and eukaryotes. It follows that investigations of archaebacterial characteristics might reveal features of early evolution. So far, two genes, one for bacteriorhodopsin and another for halorhodopsin, both from Halobacterium halobium, have been sequenced. We cloned and sequenced the gene coding for the polypeptide of another one of these rhodopsins, a halorhodopsin in Natronobacterium pharaonis. Peptide sequencing of cyanogen bromide fragments, and immuno-reactions of the protein and synthetic peptides derived from the C-terminal gene sequence, confirmed that the open reading frame was the structural gene for the pharaonis halorhodopsin polypeptide. The flanking DNA sequences of this gene, as well as those of other bacterial rhodopsins, were compared to previously proposed archaebacterial consensus sequences. In pairwise comparisons of the open reading frame with DNA sequences for bacterio-opsin and halo-opsin from Halobacterium halobium, silent divergences were calculated. These indicate very considerable evolutionary distance between each pair of genes, even in the dame organism. In spite of this, three protein sequences show extensive similarities, indicating strong selective pressures.

Lanyi, J. K.↗

Reactive Oxygen Species on the Early Earth and Survival of Bacteria

An oxygen-rich atmosphere appears to have been a prerequisite for complex, multicellular life to evolve on Earth and possibly elsewhere in the Universe. However it remains unclear how free oxygen first became available on the early Earth. A potentially important, and as yet poorly constrained pathway, is the production of oxygen through the weathering of rocks and release into the near-surface environment. Reactive Oxygen Species (ROS), as precursors to molecular oxygen, are a key step in this process, and may have had a decisive impact on the evolution of life, present and past. ROS are generated from minerals in igneous rocks during hydrolysis of peroxy defects, which consist of pairs of oxygen anions oxidized to the valence state -1 and during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that, despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, organisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defences against the potentially dangerous, even lethal effects of oxygen and its derived ROS. Conversely it appears that microorganisms learned to take advantage of the enormous reactive potential and energy gain provided by nascent oxygen. We investigate how oxygen might be released through weathering. We test microorganisms in contact with rock surfaces and iron sulphides. We model bacteria such as Deionococcus radiodurans and Desulfotomaculum, Moorella and Bacillus species for their ability to grow or survive in the presence of ROS. We examine how early Life might have adapted to oxygen.

Balk, Melikea↗

The evolution of ClO and NO along air parcel trajectories

Back trajectory analysis of Arctic and Antarctic aircraft data reveals that high ClO concentrations are associated with predicted polar stratospheric cloud (PSCs) encounters. The ClO concentrations within the Arctic and Antarctic polar vortices vary widely but appear to be inversely related to parcel solar exposure since the last PSC interaction. These results imply that production of NO(x) from HNO3 photolysis and reaction with OH is the mechanism for the loss of chlorine radicals through the reformation of chlorine nitrate. Highly denitrified air parcels show no change in ClO with solar exposure. The recovery process is quantitatively duplicated using a model of chemistry along trajectories. Although PSC processing is the primary mechanism for producing elevated ClO amounts, back trajectories apparently unperturbed by PSC's also show slightly elevated ClO levels in 1992 compared to Arctic 1989 and Antarctic 1987 measurements presumably due to the presence of Pinatubo aerosol.

Schoeberl, M. R.↗

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.↗

Catalysts for electrochemical generation of oxygen

Several aspects of the electrolytic evolution of oxygen for use in life support systems are analyzed including kinetic studies of various metal and nonmetal electrode materials, the formation of underpotential films on electrodes, and electrode surface morphology and the use of single crystal metals. In order to investigate the role of surface morphology to electrochemical reactions, a low energy electron diffraction and an Auger electron spectrometer are combined with an electrochemical thin-layer cell allowing initial characterization of the surface, reaction run, and then a comparative surface analysis.

Hagans, P.↗

CNO isotope production in nova outbursts

A current model of novae is presented which explains their outbursts assuming that the progenitor of a common nova is a carbon-oxygen dwarf. This white dwarf accretes H-rich material from its companion which produces strong shock waves at its surface; as the amount of accreted material increases later, its bottom ignites. The nova outburst is then triggered by CNO-Ne reactions which favor the formation of rare isotopes with proton-rich radioactive parents such as C-13, N-15, O-17, and Ne-21. The production of such nuclear species is examined in different nova models, and conclusions are drawn concerning the importance of novae in models of chemical evolution of the galaxy.

Audouze, J.↗

Heterogeneous physicochemistry of the polar ozone hole

Processes occurring in the polar winter stratosphere, which involve polar stratospheric clouds (PSCs), are investigated using observations from the Airborne Antarctic Ozone Experiment. In particular, data on the properties of PSCs and their physical chemistry, the microphysical processes and time constants for cloud processes, the heterogeneous chemical processes and their time constants, and nonlinearities in the long-term ozone trend associated with physical and chemical processes are examined. The chemical reactions leading to the depletion of the inert chlorine reservoir in a presence of type I PSCs are established, and it is shown that type II PSCs contribute to chemical processing that sustains the chemical imbalance of the polar stratosphere. It is shown that, using a simple model, the decadal evolution of the Antarctic ozone hole may be understood through nonlinearities in the heterogeneous chemistry, with possible contributing effects of variations in stratospheric temperatures and water vapor concentrations.

Turco, Richard P.↗

Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA

The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions. c2005 COSPAR. Published by Elsevier Ltd. All rights reserved.

Amino Acids/chemistry↗

Primordial organic chemistry and the origin of life.

Aspects of Darwinian revolution are discussed together with spontaneous generation, the inorganic chemical evolution, the primitive atmosphere, and interstellar matter. The significance of the change of the earth's reducing atmosphere to an atmosphere with oxidizing characteristics is considered. Experiments regarding the abiogenic synthesis of nucleic acids and proteins are reported. It was found that micromolecules can be formed in simulation experiments. The condensation reaction taking place in the presence of water was studied together with the condensation reaction taking place in the relative absence of water or under hypohydrous conditions. Jupiter simulation studies were conducted, and lunar and meteorite material was analyzed.

Ponnamperuma, C.↗

An evaluation of discarded tires as a potential source of fuel

The destructive distillation of rubber tire samples was studied by thermogravimetry, differential scanning calorimetry, combustion calorimetry, and mass spectroscopy. The decomposition reaction was found to be exothermic and produced a mass loss of 65%. The products from the distillation process were a solid residue with a heating value of about -30 MJ/kg, a liquid with a heating value of about -40 MJ/kg, and a combustible gas of undetermined heating value. The gas evolution curves which were obtained indicate that a variety of organic materials are evolved simultaneously during decomposition of the rubber polymer.

Collins, L. W.↗

Formation of Benzene in the Interstellar Medium

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.

Jones, Brant M.↗

Micropump Technology and Applications

This paper describes reversed engineered biological peristaltics through the insightful evolution of MEMS technology. While the emphasis on pump applications is in the miniaturization of spacecraft bus and payload, terrestrial applications are evident.

peristaltics↗

Airborne Lidar Measurements of Ozone and Aerosol Profiles Over Major US Metropolitan Areas

During field missions in 2021 and 2023, the airborne NASA Langley Research Center High Spectral Resolution Lidar 2 (HSRL 2) measured the temporal and spatial evolution of ozone and aerosol distributions impacting urban air quality over the four most populated cities in the United States. HSRL-2 measurements in 2021 were acquired over the Houston metropolitan region, including Galveston Bay and the Houston Ship Channel, as part of the NASA Tracking Aerosol Convection Experiment – Air Quality (TRACER-AQ) mission conducted in collaboration with the Department of Energy. HSRL-2 measurements were acquired over Los Angeles, Chicago, and New York City in 2023 as part of the NASA Synergistic TEMPO Air Quality Science (STAQS) mission conducted in collaboration with the NOAA Atmospheric Emissions and Reactions Observed from Megacities to Marine Areas (AEROMMA) mission. HSRL 2 provided nadir vertical profiles of ozone, aerosol backscatter, extinction, and depolarization as the aircraft flew lawnmower type patterns at 9 km for several hours over these urban areas. HSRL-2 measured profiles of aerosol extinction and aerosol optical depth (AOD) via the HSRL technique at 355 and 532 nm and profiles of aerosol backscatter and depolarization at 355, 532, and 1064 nm. Mixed Layer Heights (MLH) were derived by locating sharp vertical gradients in the profiles of aerosol backscatter. The flights were comprised of up to three repeating lawnmower patterns over each city showing the evolution of the ozone and aerosol distributions from the morning through the afternoon. The HSRL-2 measurements reveal ozone enhancements near the surface as well as in the free troposphere above the mixed layer. Some lidar measurements over Chicago and New York City show the daytime boundary layer growing into elevated layers of biomass burning aerosol. These layers complicate efforts to use column-integrated satellite measurements to infer surface air quality. As expected, mixed layer height (MLH) typically increased significantly during the day; however, during some flights, particularly over the Houston area, MLH also showed large spatial variability associated with changes in surface cover and/or small scale circulations. Often HSRL-2 measurements of AOD also showed large spatial and temporal variability throughout the day over these cities. We discuss how the ozone and aerosol profiles are averaged over different vertical and horizontal scales near the surface for use in assessments of regional air quality models and near-surface ozone retrievals from NASA’s recently launched Tropospheric Emissions: Monitoring Pollution (TEMPO) satellite.

Lidar↗