The Cryogenic Prebiotic Chemistry of Titan

Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

Authors:

Rahm et al

Abstract:

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini–Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N–H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

Atmospheric Organic Polymers may be Raining out on Titan, Contributing to Titan's Dunes

Electron-molecule chemistry and charging processes on organic ices and Titan’s icy aerosol surrogates

Authors:

Pirim et al

Abstract:

Electron-induced polymerization processes and charging events that can occur within Titan’s atmosphere or on its surface were simulated using electron irradiation and dissociative electron attachment (DEA) studies of nitrogen-containing organic condensates. The DEA studies probe the desorption of H− from hydrogen cyanide (HCN), acetonitrile (CH3CN), and aminoacetonitrile (NH2CH2CN) ices, as well as from synthesized tholin materials condensed or deposited onto a graphite substrate maintained at low temperature (90–130 K). The peak cross sections for H− desorption during low-energy (3–15 eV) electron irradiation were measured and range from 3 × 10−21 to 2 × 10−18 cm2. Chemical and structural transformations of HCN ice upon 2 keV electron irradiation were investigated using X-ray photoelectron and Fourier-transform infrared spectroscopy techniques. The electron-beam processed materials displayed optical properties very similar to tholins produced by conventional discharge methods. Electron and negative ion trapping lead to 1011 charges cm−2 on a flat surface which, assuming a radius of 0.05 μm for Titan aerosols, is ∼628 charges/radius (in μm). The facile charge trapping indicates that electron interactions with nitriles and complex tholin-like molecules could affect the conductivity of Titan’s atmosphere due to the formation of large negative ion complexes. These negatively charged complexes can also precipitate onto Titan’s surface and possibly contribute to surface reactions and the formation of dunes.

Thermal Degradation of Titan's Atmospheric Organics

Thermal degradation of organics for pyrolysis in space: Titan’s atmospheric aerosol case study

Authors:

He et al

Abstract:

Pyrolysis coupled with mass spectry is among the instrumentation the most implemented in planetary exploration probes to analyze the chemical composition of extraterrestrial solid samples. It is used to analyze the volatile species which can be thermally extracted from the samples, including the organic fraction which is of primary interest for astrobiological purposes. However the thermal degradation of these organic materials, which can be very complex in nature or very different from organics commonly present on Earth, is badly known. This leads to a restriction in the optimization of space instrumentation, and in the interpretation of the measurements. In the present work we propose a complete overview of the thermal degradation processes studied on a model of complex organic material produced in an extraterrestrial environment, i.e. laboratory analogues of Titan’s atmospheric aerosols. The thermal evolution of the studied analogues is monitored by following their mass loss, the emitted heating flux, and the evolution of their chemical composition through infrared spectroscopy and elemental analysis. The gaseous products released from the material are also analyzed by mass spectrometry, allowing to better constrain the mechanisms of chemical evolution of the samples. The complex organic material analyzed is found not to be fully decomposed when heated up to about 800 °C, with the evidence that nitrogen is still deeply incorporated in the remaining graphitic carbon nitride residue. The most appropriate pyrolysis temperature to chemically probe the studied material is found to be about 450 °C because at this temperature are detected the largest gaseous molecules which should be the most representative ones of the material pyrolyzed.

What Happens to Complex Organic Molecules Under Martian Conditions?

Laboratory insights into the chemical and kinetic evolution of several organic molecules under simulated Mars surface UV radiation conditions

Authors:

Poch et al

Abstract:

The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars’ exploration. Understanding the chemical evolution of organic molecules under current martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? This paper presents the results of laboratory investigations dedicated to monitor the evolution of organic molecules when submitted to simulated Mars surface ultraviolet radiation (190–400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) conditions. Experiments are done with the MOMIE simulation setup (for Mars Organic Molecules Irradiation and Evolution) allowing both a qualitative and quantitative characterization of the evolution the tested molecules undergo (Poch, O. et al. [2013]. Planet. Space Sci. 85, 188–197). The chemical structures of the solid products and the kinetic parameters of the photoreaction (photolysis rate, half-life and quantum efficiency of photodecomposition) are determined for glycine, urea, adenine and chrysene. Mellitic trianhydride is also studied in order to complete a previous study done with mellitic acid (Stalport, F., Coll, P., Szopa, C., Raulin, F. [2009]. Astrobiology 9, 543–549), by studying the evolution of mellitic trianhydride. The results show that solid layers of the studied molecules have half-lives of 10–103 h at the surface of Mars, when exposed directly to martian UV radiation. However, organic layers having aromatic moieties and reactive chemical groups, as adenine and mellitic acid, lead to the formation of photoresistant solid residues, probably of macromolecular nature, which could exhibit a longer photostability. Such solid organic layers are found in micrometeorites or could have been formed endogenously on Mars. Finally, the quantum efficiencies of photodecomposition at wavelengths from 200 to 250 nm, determined for each of the studied molecules, range from 10−2 to 10−6 molecule photon−1 and apply for isolated molecules exposed at the surface of Mars. These kinetic parameters provide essential inputs for numerical modeling of the evolution of Mars’ current reservoir of organic molecules. Organic molecules adsorbed on martian minerals may have different kinetic parameters and lead to different endproducts. The present study paves the way for the interpretation of more complex simulation experiments where organics will be mixed with martian mineral analogs.