Enrichment of the amino acid L-isovaline by aqueous alteration on CI and CM meteorite parent bodies

The distribution and enantiomeric composition of the 5-carbon (C(5)) amino acids found in CI-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/N-acetyl- L-cysteine derivatization. A large L-enantiomeric excess (ee) of the alpha-methyl amino acid isovaline was found in the CM meteorite Murchison (L(ee) = 18.5 +/- 2.6%) and the CI meteorite Orgueil (L(ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any CI meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered CI and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.