Photocatalytic decomposition of carboxylated molecules on light-exposed martian regolith and its relation to methane production on Mars.
We propose that the paucity of organic compounds in martian soil can be accounted for by efficient photocatalytic decomposition of carboxylated molecules due to the occurrence of the photo-Kolbe reaction at the surface of particulate iron(III) oxides that are abundant in the martian regolith. This photoreaction is initiated by the absorption of UVA light, and it readily occurs even at low temperature. The decarboxylation is observed for miscellaneous organic carboxylates, including the nonvolatile products of kerogen oxidation (that are currently thought to accumulate in the soil) as well as alpha-amino acids and peptides. Our study indicates that there may be no "safe haven" for these organic compounds on Mars; oxidation by reactive radicals, such as hydroxyl, is concerted with photocatalytic reactions on the oxide particles. Acting together, these two mechanisms result in mineralization of the organic component. The photooxidation of acetate (the terminal product of radical oxidation of the aliphatic component of kerogen) on the iron(III) oxides results in the formation of methane; this reaction may account for seasonably variable production of methane on Mars. The concomitant reduction of Fe(III) in the regolith leads to the formation of highly soluble ferrous ions that contribute to weathering of the soil particles.
Shkrob
Ilya A
IA
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA. shkrob@anl.gov
Chemerisov
Sergey D
SD
Marin
Timothy W
TW
D000596:Amino Acids / Q000032:analysis; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis / Q000528:radiation effects; D004578:Electron Spin Resonance Spectroscopy; D005118:Extraterrestrial Environment; D019015:Geologic Sediments / Q000737:chemistry*; D008027:Light; D018535:Mars; D008697:Methane / Q000138:chemical synthesis*; D010455:Peptides / Q000032:analysis; D014466:Ultraviolet Rays
D000596:Amino Acids; D002264:Carboxylic Acids; D010455:Peptides; D008697:Methane