Combined IR and XPS characterization of organic refractory residues obtained by ion irradiation of simple icy mixtures

Abstract

Context. Multi-year laboratory experiments have demonstrated that frozen icy mixtures containing simple organic and inorganic molecules (such as H2O, N2, CH4, CO, CO2, C2H6, etc.), if exposed to a flux of energetic ions or UV photons, give rise to new more complex molecules at low temperatures (10–50 K). A fraction of the new synthesized molecules is volatile while the remaining fraction is refractory and therefore it is preserved after the warm-up of the substrate to room temperature. Moreover, a part of the refractory material is formed during the annealing to room temperature, when molecules and radicals into the processed ice become mobile and react to form non-volatile molecules. By means of similar mechanisms, complex organic materials may be formed on the icy surfaces of some objects in the outer solar system, such as trans-Neptunian objects, comets and some satellites of the giant planets: in fact the interaction with solar wind and solar flares ions, solar photons and galactic cosmic rays could produce more refractory materials, analogous to those produced in the laboratory. In some cases, the materials thus synthesized may contain functional groups considered relevant to the pre-biotic chemistry in the hypothesis that interplanetary dust particles, comets and meteoroids contributed to seed the early Earth with the building blocks of life. Aims. The aim of this work is to investigate the chemical similarities and differences between some organic residues left over after ion bombardment (200 keV H+) of different ice mixtures followed by subsequent warm up under vacuum to room temperature. Methods. Seven organic residues have been prepared in our laboratory following a procedure involving the proton irradiation of seven different icy mixtures and their warm-up to room temperature. All the organic samples were characterized by FTIR spectroscopy with measurements performed in situ, in the ultra-high vacuum condition preventing any sample degradation. Three of them were selected to be characterized by XPS spectroscopy as well. Results. Among the organic residues presented in this paper, only those containing nitrogen and carbon exhibit the multi-component band centred at 2200 cm−1. This multi-component band presents interest from the astrobiological point of view due to its attribution to nitriles (–C≡N) and isonitriles (–N≡C). Our results demonstrate that this band is present in the IR spectra of organic nitrogen residues regardless the use of oxygen-bearing species in the icy mixture. This finding is of interest since the 2200 cm−1 band has been observed in some extraterrestrial samples (micro-meteorites) collected in the Antarctica.