Extraterrestrial Amino Acids and Amines Identified in Asteroid Ryugu Samples Returned by the Hayabusa2 Mission

Eric T. Parker, Hannah L. McLain, Daniel P. Glavin, Jason P. Dworkin, Jamie E. Elsila, José C. Aponte, Hiroshi Naraoka, Yoshinori Takano, Shogo Tachibana, Hikaru Yabuta, Hisayoshi Yurimoto, Kanako Sakamoto, Toru Yada, Masahiro Nishimura, Aiko Nakato, Akiko Miyazaki, Kasumi Yogata, Masanao Abe, Tatsuaki Okada, Tomohiro Usui, Makoto Yoshikawa, Takanao Saiki, Satoshi Tanaka, Satoru Nakazawa, Yuichi Tsuda, Fuyuto Terui, Takaaki Noguchi, Ryuji Okazaki, Sei-ichiro Watanabe, Tomoki Nakamura

Geochimica et Cosmochimica Acta
In Press, Journal Pre-proof, Available online 24 February 2023


“The hot water and acid extracts of two different Ryugu samples collected by the Hayabusa2 mission were analyzed for the presence of aliphatic amines and amino acids. The abundances and relative distributions of both classes of molecules were determined, as well as the enantiomeric compositions of the chiral amino acids. The Ryugu samples studied here were recovered from sample chambers A and C, which were composed of surface material, and a combination of surface and possible subsurface material, respectively. A total of thirteen amino acids were detected and quantitated in these samples, with an additional five amino acids that were tentatively identified but not quantitated. The abundances of four aliphatic amines identified in the Ryugu samples were also determined in the current work. Amino acids were observed in the acid hydrolyzed and unhydrolyzed hot water extracts of asteroid Ryugu regolith using liquid chromatography with UV fluorescence detection and high-resolution mass spectrometry. Conversely, aliphatic amines were only analyzed in the unhydrolyzed hot water Ryugu extracts. Two- to six-carbon (C2-C6) amino acids with individual abundances ranging from 0.02–15.8 nmol g-1, and one- to three-carbon (C1-C3) aliphatic amines with individual abundances from 0.05–34.14 nmol g-1, were found in the hot water extracts. Several non-protein amino acids that are rare in biology, including β-amino-n-butyric acid (β-ABA) and β-aminoisobuytric acid (β-AIB), were racemic or very nearly racemic, thus indicating their likely abiotic origins. Trace amounts of select protein amino acids that were enriched in the l-enantiomer may indicate low levels of terrestrial amino acid contamination in the samples. However, the presence of elevated abundances of free and racemic alanine, a common protein amino acid in terrestrial biology, and elevated abundances of the predominately free and racemic non-protein amino acids, β-ABA and β-AIB, indicate that many of the amino acids detected in the Ryugu water extracts were indigenous to the samples. Although the Ryugu samples have been found to be chemically similar to CI type carbonaceous chondrites, the measured concentrations and relative distributions of amino acids and aliphatic amines in Ryugu samples were notably different from those previously observed for the CI1.1 carbonaceous chondrite, Orgueil. This discrepancy could be the result of differences in the original chemical compositions of the parent bodies and/or alteration conditions, such as space weathering. In addition to α-amino acids that could have been formed by Strecker cyanohydrin synthesis during a low temperature aqueous alteration phase, β-, γ-, and δ-amino acids, including C3 – C5 straight-chain n-ω-amino acids that are not formed by Strecker synthesis, were also observed in the Ryugu extracts. The suite of amino acids measured in the Ryugu samples indicates that multiple amino acid formation mechanisms were active on the Ryugu parent body. The analytical techniques used here are well-suited to search for similar analytes in asteroid Bennu material collected by the NASA OSIRIS-REx mission scheduled for Earth return in September 2023.”