Benjamin Fleury

Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young solar system and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan’s atmosphere and in the protosolar nebula, respectively. The nitrogen content, the N speciation and the N isotopic composition were analyzed in the resulting organic aerosols. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25 ‰ relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among solar system objects and reservoirs. Extreme N isotope signatures in the solar system are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan’s atmosphere. In the Titans night side, 15N-depletion resulting from electron driven reactions would counterbalance photo-induced 15N enrichments occurring on the days side. Kinetic N isotope fractionation may also be responsible for the lower δ15N values of Archean sediments compared to Proterozoic-Phanerozoic values (Beaumont and Robert, 1999). We suggest that the low δ15N values of Archean organics are partly the result of abiotic synthesis of organics that occurred at that time, and that the subsequent development of the biosphere resulted in shifts of δ15N towards higher values.

Water formation in the upper atmosphere of the early Earth

The water concentration and distribution in the early Earths atmosphere are important parameters that contribute to the chemistry and the radiative budget of the atmosphere. If the atmosphere above the troposphere is generally considered as dry, photochemistry is known to be responsible for the production of numerous minor species. Here we used an experimental setup to study the production of water in conditions simulating the chemistry above the troposphere of the early Earth with an atmospheric composition based on three major molecules: N2, CO2, and H2. The formation of gaseous products was monitored using infrared spectroscopy. Water was found as the major product, with approximately 10% of the gas products detected. This important water formation is discussed in the context of the early Earth.

Organic chemistry in a CO 2 rich early Earth atmosphere

Abstract The emergence of life on the Earth has required a prior organic chemistry leading to the formation of prebiotic molecules. The origin and the evolution of the organic matter on the early Earth is not yet firmly understood. Several hypothesis, possibly complementary, are considered. They can be divided in two categories: endogenous and exogenous sources. In this work we investigate the contribution of a specific endogenous source: the organic chemistry occurring in the ionosphere of the early Earth where the significant VUV contribution of the young Sun involved an efficient formation of reactive species. We address the issue whether this chemistry can lead to the formation of complex organic compounds with CO2 as only source of carbon in an early atmosphere made of N2, CO2 and H2, by mimicking experimentally this type of chemistry using a low pressure plasma reactor. By analyzing the gaseous phase composition, we strictly identified the formation of H2O, NH3, N2O and C2N2. The formation of a solid organic phase is also observed, confirming the possibility to trigger organic chemistry in the upper atmosphere of the early Earth. The identification of Nitrogen-bearing chemical functions in the solid highlights the possibility for an efficient ionospheric chemistry to provide prebiotic material on the early Earth.