Highest molecular diversity and structural complexity revealed with ultrahigh resolution
mass spectrometry and nuclear magnetic resonance spectroscopy of Ryugu´s samples
Philippe Schmitt-Kopplin1, 2, Norbert Hertkorn2, Marianna Lucio2, Marco Matzka2, Mourad Harir2,
Philippe Diederich2, Hiroshi Naraoka3, Hisayoshi Yurimoto4, Tomoki Nakamura5, Takaaki Noguchi6,
Ryuji Okazaki3, Hikaru Yabuta7, Kanako Sakamoto8, Shogo Tachibana8,9, Seiichiro Watanabe10 and Yuichi Tsuda8
and the Hayabusa2-initial-analysis SOM team1

Technische Universität Muenchen, Germany, 2 Helmholtz Zentrum Muenchen, Germany,
3Kyushu Univ., Japan, 4Hokkaido Univ., Japan, 5Tohoku Univ., Japan, 6Kyoto Univ., Japan,7Hiroshima Univ., Japan, 8JAXA, Japan, 9Univ. Tokyo, Japan, 10Nagoya Univ., Japan.

The surface and possible sub-surface materials of the asteroid Ryugu were recovered during the two touch-down
sampling by the Hayabusa2 spacecraft. Here we present the first results on the solvent soluble organic matter (SOM)
using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectroscopy (FTICR/MS) complemented
with high field nuclear magnetic resonance spectroscopy (NMR) [1-3]. The two samples A106 (first touchdown) andC107 (second touchdown) were sequentially extracted in the Hayabusa2-initial-analysis SOM team with various polar
and apolar solvent extracts and demonstrate a never seen molecular complexity and diversity.
We confirm herewith the close similarity and the possible comparison of the solvent extracts with meteoritic
material to the Hayabusa2 return samples. We analyzed the sequential hexane, dichloromethane (DCM), methanoland water extracts with NMR and with electrospray ionization (ESI) and atmospheric pressure photoionization (APPI)[4] FTICR/MS systematically for both negative and positive ions. The hundred thousands of signals were filtered,converted and assigned into more than 24,000 elementary compositions consisting of carbon (C), hydrogen (H),nitrogen (N), oxygen (O) and/or sulfur (S). Organomagnesium compounds (CHOMg, CHOSMg) were not found andthis reflects the low temperature processes on the parent body [5, 6]. As shown for carbonaceous chondrites previously,
our results confirm that the extraterrestrial chemical diversity is much higher compared to terrestrial biological andbiogeochemical spaces and consists in a regular continuum (i) of small to macromolecules (ii) of carbon oxidation
states from apolar (CH, polycyclic aromatic hydrocarbons and branched aliphatics) to polar small molecules (CHO)
with increasing functionalized oxygen and heteroatom contents (CHN, CHS, CHNO, CHOS) leading to the observed
differential solvent type solubility. We revealed specific known molecular targets (CHN+, CHNO+) [4] and show
evidences of multiple chemosynthesis pathways in describing the carbon oxidation state distribution and heteroatom
contributions to the assembly of multiple complex endogen molecules; these also reflect cold hydrothermalism
involved on the parent body [5,6]. We also confirm the high importance of chemical processes involving specificnitrogen and sulfur chemistry [7, 8]. The two fractions analyzed show an extreme coverage in structural features in
APPI and only slight differences in the apolar solvents in ESI. The A106 sample showed slight differences only withhigher mass range and more oxygenated compounds. The C107 sample had increased abundance and uniqueness ofmore unsaturated carbon and low oxygenated compounds that may have disappeared due to surface processing (somehypothesis could be cosmic irradiation at the surface). These samples presents a unique opportunity of having a direct
and low invasive insight into the complex organic diversity present on 162173 Ryugu.

Figure 1. Selected results from the analysis of the solvent extracts of A106 (24159 formula) and C107 (23250 formula) analyzed
with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) in electrospray ionization negative mode (ESI(-))
and atmospheric pressure photoionization (APPI(+)). (A) nominal mass 319 details of dichloromethane (DCM) extracts of the CM2Aguas Zarcas, A106, C107 and the DCM-blank with the annotated elementary compositions as CH, CHO and CHNO fromultrahigh resolution. (B) counting of the thousands of elementary compositions in the C, H, O, N, S space as obtained from ESI(-)
and APPI(+) and there abundance variations within the different extraction solvents for the A106 and C107 samples. (C)visualization of the structural information retrieved from the elementary compositions as van Krevelen diagram plots describing
the differences in oxygenations between the two ionization modes ESI(-) and APPI(+) and the profiles of the non-oxygenated CH,CHS and CHN compounds.

References[1] Schmitt-Kopplin, P. et al. 2010. Proc. Natl. Acad. Sci. U.S.A., 107:2763. [2] Ruf, A. et al. 2018. Life 8:18. [3]Hertkorn, N. et al. 2015 Magn. Reson. Chem., 53:754. [4] Herzog J. et al. 2019. Life, 9:48. [5] Ruf. A. et al. 2017 Proc.
Natl. Acad. Sci. U.S.A., 2017, 114:2819. [6] Matzka, M. et al. 2021. Astrophys. J. Lett., 915:L7. [7] Danger, G. et al.
2021. Nat. Commun., 12:1. [8] Danger, G. et al. 2020. Planet. Space Sci., 1:55.