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Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

King, C.-C.

Conducting Miller-Urey Experiments

In 1953, Stanley Miller reported the production of biomolecules from simple gaseous starting materials, using apparatus constructed to simulate the primordial Earth's atmosphere-ocean system. Miller introduced 200 ml of water, 100 mmHg of H2, 200mmHg of CH4, and 200mmHg of NH3 into the apparatus, then subjected this mixture, under reflux, to an electric discharge for a week, while the water was simultaneously heated. The purpose of this manuscript is to provide the reader with a general experimental protocol that can be used to conduct a Miller-Urey type spark discharge experiment, using a simplified 3 L reaction flask. Since the experiment involves exposing inflammable gases to a high voltage discharge, it is worth highlighting important steps that reduce the risk of explosion. The general procedures described in this work can be extrapolated to design and conduct a wide variety of electric discharge experiments simulating primitive planetary environments.

Prebiotic chemistry

Amino Acids Generated from Hydrated Titan Tholins: Comparison with Miller-Urey Electric Discharge Products

Various analogues of Titan haze particles (termed tholins) have been made in the laboratory. In certain geologic environments on Titan, these haze particles may come into contact with aqueous ammonia (NH3) solutions, hydrolyzing them into molecules of astrobiological interest. A Titan tholin analogue hydrolyzed in aqueous NH3 at room temperature for 2.5 years was analyzed for amino acids using highly sensitive ultra-high performance liquid chromatography coupled with fluorescence detection and time-of-flight mass spectrometry (UHPLC-FDToF-MS) analysis after derivatization with a fluorescent tag. We compare here the amino acids produced from this reaction sequence with those generated from room temperature Miller-Urey (MU) type electric discharge reactions. We find that most of the amino acids detected in low temperature MU CH4N2H2O electric discharge reactions are generated in Titan simulation reactions, as well as in previous simulations of Triton chemistry. This argues that many processes provide very similar mixtures of amino acids, and possibly other types of organic compounds, in disparate environments, regardless of the order of hydration. Although it is unknown how life began, it is likely that given reducing conditions, similar materials were available throughout the early Solar System and throughout the universe to facilitate chemical evolution.

Astrobiology aEuro" Titan

The Origin of Organic Matter in the Solar System: Evidence from Interplanetary Dust Particles

The origin of the organic matter in interplanetary materials has not been established. A variety of mechanisms have been proposed, with two extreme cases being a Fisher-Tropsch type process operating in the gas phase of the solar nebula or a Miller-Urey type process, which requires interaction with an aqueous fluid, presumably occurring on an asteroid. In the Fisher-Tropsch case, we might expect similar organic matter in hydrated and anhydrous interplanetary materials. However, aqueous alteration is required in the case of the Miller-Urey process, and we would expect to see organic matter preferentially in interplanetary materials that exhibit evidence of aqueous activity, such as the presence of hydrated silicates. The types and abundance of organic matter in meteorites have been used as an indicator of the origin of organic matter in the Solar System. Indigenous complex organic matter, including amino acids, has been found in hydrated carbonaceous chondrite meteorites, such as Murchison. Much lower amounts of complex organic matter, possibly only terrestrial contamination, have been found in anhydrous carbonaceous chondrite meteorites, such as Allende, that contain most of their carbon in elemental form. These results seem to favor production of the bulk of the organic matter in the Solar System by aqueous processing on parent bodies such as asteroids, a Miller-Urey process. However, the hydrated carbonaceous chondrite meteorites have approximately solar abundances of the moderately volatile elements, while all anhydrous carbonaceous chondrite meteorites have significantly lower contents of these moderately volatile elements. Two mechanisms, incomplete condensation or evaporation, both of which involve processing at approx. 1200 C, have been suggested to explain the lower content of the moderately volatile elements in all anhydrous meteorites. Additional information is contained in the original extended abstract.

Flynn, G. J.

Isotopic characterisation of prebiotic synthesis of organic material

Many primitive meteorites contain an insoluble organic material, much like terrestrial kerogen, whose mode of origin is currently unknown. When sujbected to stepwise decomposition, this material, unlike its terrestrial counterpart, reveals characteristic release patterns for the stable isotopes of carbon, hydrogen and nitrogen as a function of fractional release of each element. The purpose of this study is to try to match those release patterns using organic matter synthesised in the laboratory under controlled conditions. If successful, such a study would shed light on the origin of kerogen-like organic matter in the early solar system and, by extension, on prebiotic organic synthesis in general. The range of possible syntheses, starting materials and reaction conditions to be investigated is considerable. Samples analysed to date include: a heavy oil produced by Fischer-Tropsch-type catalysis of CO + H2; a solid residue generated by a plasma discharge in CO + H2 + N2; a solid deposited on the electrodes of a Miller-Urey synthesis operating on CH4 + H2O + N2; and a solid residue formed by polymerization of light hydrocarbons procured by a Miller-Urey discharge acting on CH4. Significant structure is observed in the release patterns for the carbon and hydrogen isotopes from the synthetic samples, though there is little evidence for isotopic fractionation during the analysis itself.

Kerridge, J. F.

Interstellar molecules - Formation in solar nebulae

Herbig's (1970) hypothesis that solar nebulae might be the principal source of interstellar grains and molecules is investigated. The investigation includes the determination of physical and chemical conditions in the early solar system. The production of organic compounds in the solar nebula is studied, and the compounds in meteorites are compared with those obtained in Miller-Urey and Fischer-Tropsch-type (FTT) reactions, taking into consideration aliphatic hydrocarbons, aromatic hydrocarbons, purines, pyrimidines, amino acids, porphyrins, and aspects of carbon-isotope fractionation. It is found that FTT reactions account reasonably well for all well-established features of organic matter in meteorites investigated. The distribution of compounds produced by FTT reactions is compared with the distribution of interstellar molecules. Biological implications of the results are considered.

Anders, E.

Life on Jupiter

The possibilities of life on Jupiter are discussed from the point view of life as known on earth. That is, it is assumed that any life on Jupiter would not involve new principles foreign to us. Proteins would be a constituent as would fats and the other building blocks of living organisms on earth. This leads to a set of limiting parameters, such as pressure. Studies in the laboratory have shown that proteins and other essential molecules are denatured by pressures of 4000 atm and higher. Thus, life cannot be expected to exist in the great depths of the Jovian atmosphere. It could exist only at depths of several hundred kilometers in the atmosphere. Since no solid surface could possibly exist at such altitudes, any organisms present must be small enough to be buoyed up by the turbulent atmospheric currents or must fly or both. Such possibilities, however, seem to be real. The necessary nutrients to preserve life and foster growth could be furnished by the Miller-Urey type reactions of ionizing radiation on the reducing atmosphere undoubtedly present.

Libby, W. F.

Exponential kinetics of formation of organic microstructures

Organic microstructure production in Miller-Urey spark discharge flasks is an energy-dependent, autocatalytic process which follows first order kinetics similar to microbial growth curves. These relationships hold for all three major morphological types of microstructures observed. The three types are assembled from smaller precursor subunits which associate according to a binomial distribution. These structures could have formed bounded systems in which pre-biological processes might have occurred.

Fraser, C. L.

Noble gas trapping and fractionation during synthesis of carbonaceous matter

An investigation of noble gas entrapment during synthesis of carbonaceous, macromolecular, and kerogen-like substances is presented. High molecular weight organic matter synthesized in aqueous condensation reactions contained little gas, and the composition was consistent with fractionation due to noble gas solubility in water; however, propane soot produced during a modified Miller-Urey experiment in an aritificial gas mixture contained high concentrations of trapped noble gases that displayed strong elemental fractionation from their reservoirs. It is concluded that theses experiemnts show that processes exist for synthesis of carbonaceous carriers that result in high noble gas concentrations and strong elemental fractionation at temperatures well above those required by absorption to achieve similar effects.

Frick, U.

Quantification of monocarboxylic acids from a spark discharge synthesis

A suite of sixteen monocarboxylic acids having carbon numbers 2 to 7, formed by the Miller-Urey spark discharge process, was identified and quantified by gas chromatography and mass fragmentography using a deuterium spiking technique. The molar concentration and isomeric distribution of these laboratory synthesized monocarboxylic acids are compared to those previously reported for the Murchison meteorite. They show similar trends, namely, decreasing molar concentration with increasing molecular weight, and a ratio of normal/branched isomers tending toward smaller values with increasing carbon numbers.

Yuen, G. U.

Laboratory experiments in the study of the chemistry of the outer planets

It is shown that much information about planetary chemistry and physics can be gained through laboratory work. The types of experiments relevant to planetary research concern fundamental properties, spectral/optical properties, 'Miller-Urey' syntheses, and detailed syntheses. Specific examples of studies of the chemistry in the atmosphere of Titan are described with attention given to gas phase chemistry in the troposphere and the composition of model Titan aerosols. A list of work that still needs to be done is provided.

Scattergood, Thomas W.

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin

Were Ocean Impacts an Important Mechanism to Deliver Meteoritic Organic Matter to the Early Earth? Some Inferences from Eltanin

Several workers have addressed the potential for extraterrestrial delivery of volatles, including water and complex organic compounds, to the early Earth. For example, Chyba and Sagan (1992) argued that since impacts would destroy organic matter, most extraterrestrial organics must be delivered in the fine-fractions of interplanetary dust. More recent computer simulations (Pierazzo and Chyba, 1999), however, have shown that substantial amounts of amino acids may survive the impacts of large (km-sized) comets and that this may exceed the amounts derived from IDPs or Miller-Urey synthesis in the atmosphere. Once an ocean developed on the early Earth, impacts of small ,asteroids and comets into deep-ocean basins were potentially common and may have been the most likely events to deliver large amounts of organics. The deposits of the late Pliocene impact of the Eltanin asteroid into the Bellingshausen Sea provide the only record of a deep-ocean (approx. 5 km) impact that can be used to constrain models of these events. This impact was first discovered in 1981 as an Ir anomaly in sediment cores collected by the USNS Eltanin in 1965 (Kyte et al., 1981). In 1995, Polarstem expedition ANT XII/4 made the first geological survey of the suspected impact region. Three sediment cores sampled around the San Martin seamounts (approx. 57.5S, 91 W) contained well-preserved impact deposits that include disturbed ocean sediments and meteoritic impact ejecta (Gersonde et al., 1997). The latter is composed of shock- melted asteroidal materials and unmelted meteorites. In 2001, the FS Polarstem returned to the impact area during expedition ANT XVIII/5a. At least 16 cores were recovered that contain ejecta deposits. These cores and geophysical data from the expedition can be used to map the effects of the impact over a large region of the ocean floor.

Kyte, Frank T.

Prebiotic materials from on and off the early Earth

One of the great puzzles of all time is how did life arise? It has been universally presumed that life arose in a soup rich in compounds made mostly of carbon, the kind of which we are currently composed. Where did these organic molecules come from? In this talk I will review proposed contributions to pre-biotic organic chemistry from both terrestrial processes (i.e., hydrothermal vents, Miller-Urey syntheses) and also from space. While the former is perhaps better known and more commonly taught in school, we now know that comet and asteroid dust deliver tons of organics to the Earth every day, and there is a growing consensus among scientists that molecules from space played an important role in making the Earth habitable, and perhaps even provided specific compounds that were directly related to the origin of life.

Bernstein, Max

Evidence from Meteorites for Multiple Possible Amino Acid Alphabets for the Origins of Life

A key question for the origins of life is understanding which amino acids made up the first proteins synthesized during the origins of life. The canonical set of 20 - 22 amino acids used in proteins are all alpha-amino, alpha-hydrogen isomers that, nevertheless, show considerable variability in properties including size, hydrophobicity, and ionizability. Abiotic amino acid synthesis experiments such as Miller-Urey spark discharge reactions produce a set of up to 23 amino acids, depending on starting materials and reaction conditions, with significant abundances of both alpha- and non-alpha-amino acid isomers. These two sets of amino acids do not completely overlap; of the 23 spark discharge amino acids, only 11 are used in modern proteins. Furthermore, because our understanding of conditions on the early Earth are limited, it is unclear which set(s) of conditions employed in spark discharge or hydrothermal reactions are correct, leaving us with significant uncertainty about the amino acid alphabet available for the origins of life on Earth. Meteorites, the surviving remnants of asteroids and comets that fall to the Earth, offer the potential to study authentic samples of naturally-occurring abiotic chemistry, and thus can provide an alternative approach to constraining the amino acid library during the origins of life.

Burton, A. S.