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The escape of molecular hydrogen and the synthesis of organic nitriles in planetary atmospheres.

What is the influence of hydrogen escape from the atmosphere of small planetary bodies on the synthesis of organic molecules in that atmosphere? To answer this question, laboratory experiments have been performed to study the evolution of different reducing model atmospheres submitted to electrical discharges, with and without the simulation of H2 escape. A study of mixtures of nitrogen and methane shows a very strong effect of H2 escape on the formation of organic nitriles, the only nitrogen containing organics detected in the gas phase. These are HCN, CH (triple bond) C-CN, (CN)2, CH2=CH-CN, CH3CN and CH3CH2CN. The yield of synthesis of most of these compounds is noticeably increased, up to several orders of magnitude, when hydrogen escape is simulated. The escape of H2 from the atmosphere of the primitive Earth may have played a crucial role in the formation of reactive organic molecules such as CH (triple bond) C-CN or (CN)2, which can be considered as important prebiotic precursors. These experimental results may also explain extant data concerning the nature and relative abundance of organics present in the atmosphere of Titan, a planetary satellite which may be an ideal model within our solar system for the study of organic cosmochemistry and exobiology.

Atmosphere↗

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds.

The prebiotic synthesis of organic compounds using a spark discharge on various simulated prebiotic atmospheres at 25 degrees has been studied. Methane mixtures contained H2 + CH4 + H2O + N2 + NH3 with H2/CH4 molar ratios from 0 to 4 and pNH3 = 0.1 torr. A similar set of experiments without added NH3 was performed. The yields of amino acids (1.2 to 4.7% based on the carbon) are approximately independent of the H2/CH4 ratio and the presence of added NH3, and a wide variety of amino acids are obtained. Mixtures of H2 + CO + H2O + N2 and H2 + CO2 + H2O + N2, with and without added NH3, all give about 2% yields of amino acids at H2/CO and H2/CO2 ratios of 2 to 4. For the H2/CO and H2/CO2 ratios less than 1, the yields fall off drastically to as low as 10(-3)%. Glycine is almost the only amino acid produced from CO and CO2 atmospheres. These results show that the maximum yield is about the same for the three carbon sources at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. In addition, CH4 gives a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these results indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde parallel the amino acid results, with yields of HCN and H2CO as high as 13% based on the carbon. Ammonia is also produced from N2 in experiments with no added NH3 in yields as high as 4.9%. These results show that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges. The amount of ammonia formed by hydrolysis of HCN and various nitriles may have exceeded that formed directly in electric discharges.

Amino Acids↗

Prebiotic oligodeoxynucleotide synthesis in a cyclic evaporating system at low temperatures.

Deoxynucleoside 5'-monophosphates were condensed by cyanamide or by l-ethyl-3-(3-dimethylaminopropyl) carbodiimide in the presence of ammonium chloride at 0 degree, 37 degrees or 60 degrees C through several cycles of evaporation to dryness with replenishment of all reactants at each cycle. We found that at 37 degrees or 60 degrees cyanamide gives distinctly more high molecular weight material than does carbodiimide. Indeed, the yield of condensed products for the cyanamide reaction (dimers and higher oligomers) was found to be between 60 percent and 80 percent. The molecular weight distribution of the product shifts to higher molecular weights as cycling continues at 37 degrees or 60 degrees for both condensing agents. The water soluble carbodiimide gives higher yields of low molecular weight product but much lower yields of the higher molecular weight products. At 0 degree yields of high molecular weight product were low for both condensing agents. Results of characterization of the products demonstrate the synthesis of oligodeoxynucleotides including tetramers, with 3'-5' phosphodiester linkages.

Ammonium Chloride↗

Prebiotic synthesis and reactions of nucleosides and nucleotides.

Diiminosuccinonitrile (DISN) has been investigated as a potential prebiotic phosphorylating agent. It is formed readily by the oxidation of diaminomaleonitrile (DAMN), a tetramer of HCN. DISN effects the cyclization of 3'-adenosine monophosphate to adenosine 2',3'-cyclic phosphace in up to 40% yield. The DISN-mediated phosphorylation of uridine to uridine mono-phosphate does not proceed efficiently in aqueous solution. The reaction of DISN and BrCN with uridine-5'-phosphate and uridine results in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2'- and 3'-hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3'-phosphate was investigated using homoionic montmorillonites.

Adenosine Monophosphate↗

On the role of meteoritic impacts in the formation of organic molecules.

It is suggested that the UV radiation, and shock and plasma phenomena which accompanied the hypervelocity impacts of solid bodies (meteorites and comets) onto the surface of the young Earth may have contributed to the synthesis of prebiotic organic molecules in the primitive atmosphere in a larger amount than was thought previously. The mechanisms responsible for this synthesis are discussed using information obtained from recent experimental and theoretical work on macroscopic hypervelocity impacts.

Earth, Planet↗

Hypotheses on the appearance of life on Earth (review).

It is generally accepted within the natural sciences that life emerged on Earth by a kind of proto-Darwinian evolution from molecular assemblies that were predominantly formed from the various constituents of the primitive atmosphere and hydrosphere. Evolutionary stages under discussion are: the self-organization of spontaneously formed biomolecules into early precursors of life (protobionts), their stepwise evolution via (postulated) protocells to (postulated) progenotes and the Darwinian evolution from progenotes to the three kingdoms of contemporary organisms (archaebacteria, eubacteria and eukaryotes). Considerable discrepancies between scientists have arisen because all evolutionary stages from prebiotic molecules to progenotes are entirely hypothetical and so are the postulated environmental conditions. We can only theorize that all those environmental conditions that allow the existence of the various forms of contemporary life might have allowed also the development of their precursors. Because of all these difficulties the hypothesis that life came to our planet from a remote place of our universe (panspermia) has been revived. But experimental evidence only supports the view that spores can--under favorable circumstances--survive a relatively short journey within our solar system (interplanetary transfer of life). It is extremely unlikely that spores can survive a journey of hundreds or thousands of years through interstellar space.

Amino Acids↗

The structural organization of polypeptides at the air-water interface.

The surface pressure-area isotherms generated by compressing monolayers formed by five polypeptide hormones at the air-water interface were studied. The results indicate that amphiphilic alpha-helical structures occupy the interfacial area, in agreement with predictions based only on the arrangements of the hydrophilic and hydrophobic amino-acid residues in the linear sequences of these polypeptides. The variety of such arrangements which result in the formation of stable helical structure, and their low degree of self-association, suggest that the induction of amphiphilic alpha-helical structure at suitable phase boundaries is likely to represent the earliest form of structural organization in polypeptides.

Air↗

Minimal requirements for molecular information transfer.

The information transfer properties of nucleic acids are largely due to the properties of the bases themselves, for which it would appear evolution has selected a highly favorable set of molecules. In aqueous solution, it is possible that this task can only be carried out efficiently by heterocyclic, condensed-ring structures fairly similar to the purines and pyrimidines. Alterations in backbone structure, however, whether in the mode of linkage or in the nature of the sugar residue, are much less critical. Such alternatives could have played a role in the emergence of life on Earth and should be considered likely in extraterrestrial environments. The possible existence of low-efficiency, information transfer systems based on other structures entirely (proteins, clay minerals, etc), remains an interesting speculation for which no evidence is presently available.

Aluminum Silicates↗

Microgravity particle research on the space station: the Gas-Grain Simulation Facility.

In the gravitational field on Earth, the large settling rate of micron-sized particles and the effects of gravity-induced convection prohibit many interesting studies of phenomena such as coagulation, collisions, and mutual interactions of droplets, dust grains and other particles. Examples of exobiology experiments involving these phenomena are the simulation of organic aerosol formation in Titan's atmosphere, studies of the role of comets in prebiotic chemical evolution, and simulations of carbon grain interactions in various astrophysical environments. The Gas-Grain Simulation Facility (GGSF) is a proposed Earth-orbital laboratory that will allow present ground-based experimental programs which study processes involving small particles and weak interactions to be extended to a new domain. Physics issues that scientists wishing to propose GGSF experiments must consider are reviewed in this paper. Specifically, coagulation, motion in gases and vacua, and wall deposition of particles in a microgravity environment are discussed.

Acceleration↗

Neoproterozoic variations in the C-isotopic composition of seawater: stratigraphic and biogeochemical implications.

The recent proliferation of stratigraphic studies of delta 13C variation in carbonates and organic C in later Neoproterozoic and basal Cambrian successions (approximately 850-530 Ma) indicates a strong oscillating trend in the C-isotopic composition of surface seawater. Alone, this trend does not adequately characterize discrete intervals in Neoproterozoic time. However, integrated with the vectorial signals provided by fossils and Sr-isotopic variations, C isotope chemostratigraphy facilitates the interbasinal correlation of later Neoproterozoic successions. Results of these studies are evaluated in terms of four stratigraphic intervals: (1) the Precambrian/Cambrian boundary, (2) the post-Varanger terminal Proterozoic, (3) the late Cryogenian, and (4) the early Cryogenian. Where biostratigraphic or radiometric data constrain the age of Neoproterozoic sedimentary sequences, secular variations in C and Sr isotopes can provide a level of stratigraphic resolution exceeding that provided by fossils alone. Isotopic data place strong constraints on the chemical evolution of seawater, linking it to major tectonic and paleoclimatic events. They also provide a biogeochemical framework for the understanding of the initial radiation of macroscopic metazoans, which is associated stratigraphically, and perhaps causally, with a global increase in the burial of organic C and a concomitant rise of atmospheric O2.

Canada↗

Asymmetries of nature and the origin of biomolecular handedness.

New developments in the problem of the origin of the asymmetry of the living systems are reviewed. The time of the appearance of the asymmetry was very probably during the chemical evolution. The asymmetry of weak interaction is still considered small to be the cause of chiral purity. New sources of asymmetry should also be considered, like the one proposed by Gilat.

Biological Evolution↗

Carbon dioxide sequestration in municipal solid waste incinerator (MSWI) bottom ash.

During bottom ash weathering, carbonation under atmospheric conditions induces physico-chemical evolutions leading to the pacification of the material. Fresh bottom ash samples were subjected to an accelerated carbonation using pure CO2. The aim of this work was to quantify the volume of CO2 that could be sequestrated with a view to reduce greenhouse gas emissions and investigate the possibility of upgrading some specific properties of the material with accelerated carbonation. Carbonation was performed by putting 4mm-sieved samples in a CO2 chamber. The CO2 pressure and the humidity of the samples were varied to optimize the reaction parameters. Unsieved material was also tested. Calcite formation resulting from accelerated carbonation was investigated by thermogravimetry and differential scanning calorimetry (TG/DSC) and metal leaching tests were performed. The volume of sequestrated CO2 was on average 12.5L/kg dry matter (DM) for unsieved material and 24 L/kg DM for 4mm-sieved samples. An ash humidity of 15% appeared to give the best results. The reaction was drastically accelerated at high pressure but it did not increase the volume of sequestrated CO2. Accelerated carbonation, like the natural phenomenon, reduces the dangerous nature of the material. It decreases the pH from 11.8 to 8.2 and causes Pb, Cr and Cd leaching to decrease. This process could reduce incinerator CO2 emissions by 0.5-1%.

Air Pollutants↗

Contribution of glial cells to the development of amyloid plaques in Alzheimer's disease.

Amyloid plaques appear early during Alzheimer's disease (AD), and their development is intimately linked to activated astrocytes and microglia. Astrocytes are capable of accumulating substantial amounts of neuron-derived, amyloid beta(1-42) (Abeta42)-positive material and other neuron-specific proteins as a consequence of their debris-clearing role in response to local neurodegeneration. Immunohistochemical analyses have suggested that astrocytes overburdened with these internalized materials can eventually undergo lysis, and radial dispersal of their cytoplasmic contents, including Abeta42, can lead to the deposition of a persistent residue in the form of small, GFAP-rich, astrocytic amyloid plaques, first appearing in the molecular layer of the cerebral cortex. Microglia, most of which appear to be derived from blood monocytes and recruited from local blood vessels, rapidly migrate into and congregate within neuritic and dense-core plaques, but not diffuse plaques. Instead of internalizing and removing Abeta from plaques, microglia appear to contribute to their morphological and chemical evolution by facilitating the conversion of existing soluble and oligomeric Abeta within plaques to the fibrillar form. Abeta fibrillogenesis may occur largely within tiny, tube-like invaginations in the surface plasma membrane of microglia. These results highlight the therapeutic potential of blocking the initial intracellular accumulation of Abeta42 in neurons and astrocytes and inhibiting microglia-mediated assembly of fibrillar Abeta, which is particularly resistant to degradation in Alzheimer brain.

Alzheimer Disease↗

Catalytic effects of glycine on prebiotic divaline and diproline formation.

The catalytic effects of the simple amino acid glycine on the formation of diproline and divaline in the prebiotically relevant salt-induced peptide formation (SIPF) reaction was investigated in systems of different amino acid starting concentrations and using the two enantiomeric forms of the respective amino acid. Results show an improved applicability of the SIPF reaction to prebiotic conditions, especially at low amino acid concentrations, as presumably present in a primordial scenario, and indicate excellent conditions and resources for chemical evolution of peptides and proteins on the early earth. For valine, furthermore differences in catalytic yield increase are found indicating a chiral selectivity of the active copper complex of the reaction and showing a connection to previously found enantiomeric differences in complex formation constants with amino acids.

Catalysis↗

Modelling of long-term dynamic leaching tests applied to solidified/stabilised waste.

The paper aims at simulating the closed-system dynamic leaching of a cement-based monolith containing lead with the numerical reactive transport code HYTEC in a 3D-cylindrical geometry. The model considers, simultaneously, the chemical evolution of pore water, the progression of mineralogical alteration fronts, and the concomitant release of elements from the S/S waste. In good agreement with the experiment, element releases were found to be mainly controlled by either diffusion (Na, K, and, to a lesser extent, Cl), by surface dissolution (Ca, Si) or by a mixed evolution (Pb, SO4). All of the calculated mineralogical transformations take place in a thin layer beyond the monolith surface. Consequently, modelling of Ca, Si and SO4 releases was quite sensitive to the node size of the simulation grid and was improved by taking into account the increase of porosity and effective diffusion coefficient due to mineral dissolution in the leached layer. In agreement with experimental results, the deepest front corresponds under closed-system conditions to portlandite dissolution and calcium silicate hydrates CSH 1.8 transformation into CSH of lower Ca/Si ratio. A second, distinct and intermediate, front is made by ettringite dissolution. The network of CSH is globally preserved in the leached layer, complete dissolution occurring over a very small thickness only. Finally, hydrotalcite precipitation in the leached layer is expected by modelling due to pH drop.

Environmental Pollutants↗

Evolution of the atmosphere.

Planetary atmospheres depend fundamentally upon their geochemical inventory, temperature and the ability of their gravitational field to retain gases. In the case of Earth and other inner planets, early outgassing released mainly carbon dioxide and water vapour. The secondary veneer of comets and meteorites added further volatiles. Photodissociation caused secondary changes, including the production of traces of oxygen from water. Earth's gravity cannot retain light gases, including hydrogen. but retains oxygen. Water vapour generally does not pass the cold trap at the stratopause. In the archaean, early evolution of life, probably in hydrothermal vents, and the subsequent development of photosynthesis in surface waters, produced oxygen, at 3500 Ma or even earlier, becoming a significant component of the atmosphere from about 2000 Ma. Thereafter banded iron formations became rare, and iron was deposited in oxidized red beds. Atmospheric levels of carbon dioxide and oxygen have varied during the Phanerozoic: major changes may have caused extinctions. particularly the Permian/Triassic. The declining greenhouse effect due to the long-term decrease in carbon dioxide has largely offset increasing solar luminosity, and changes in carbon dioxide levels relate strongly to cycles of glaciation.

Atmosphere↗

Why exobiology on Mars?

Processing of organic molecules by liquid water was probably an essential requirement towards the emergence of terrestrial primitive life. According to Oparin's hypothesis, organic building blocks required for early life were produced from simple organic molecules formed in a primitive reducing atmosphere. Geochemists favour now a less reducing atmosphere dominated by carbon dioxide. In such an atmosphere, very few building blocks are formed. Import of extraterrestrial organic molecules may represent an alternative supply. Experimental support for such an alternative scenario is examined in comets, meteorites and micrometeorites. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars attesting the presence of an atmosphere capable of decelerating C-rich micro-meteorites. Therefore, primitive life may have developed on Mars, as well. Liquid water disappeared from the surface of Mars very early, about 3.8 Ga ago. The Viking missions did not find, at the surface of the Martian soil, any organic molecules or clear-cut evidence for microbial activities such as photosynthesis, respiration or nutrition. The results can be explained referring to an active photochemistry of Martian soil driven by the high influx of solar UV. These experiments do not exclude the existence of organic molecules and fossils of micro-organisms which developed on early Mars until liquid water disappeared. Mars may store below its surface some well preserved clues of a still hypothetical primitive life.

Earth, Planet↗