Pyrrhotites in asteroid 162173 Ryugu: Records of the initial changes on their surfaces with aqueous alteration

The surface chemistry of pyrrhotites from intact particles directly collected from asteroid (162173) Ryugu was investigated by micro-Raman spectroscopy. The Raman peak characteristic to pyrrhotite was observed at around 115 cm-1 in Ryugu pyrrhotites, similar to freshly cleaved surfaces of terrestrial pyrrhotites. Additional Raman bands centered at around 220, 275, and 313 cm-1 with broadened features were also detected from the Ryugu pyrrhotites. The set of Raman bands at 220 and 275 cm-1 was assigned to typical Fe-S stretching vibrations of nu 2 (225 cm-1 ) and nu 1 (275 cm-1 ). These bands are not clearly observed in bulk crystals of pyrrhotite but appear in its nanoparticulate phase. These bands are ordinarily seen in amorphous monosulfides that formed under low oxygen fugacity ( f O 2 ) conditions in nature, indicating that the structural alteration of pyrrhotite surfaces occurred heterogeneously on the nanoscale under low f O 2 conditions. Further, the Raman band at 313 cm-1 was attributed to a characteristic tetrahedral bonding of Fe(III) in the lattice of Fe II 1-3x Fe III 1-2x S, followed by the local breakdown of the crystal lattice structures from planar bonding with Fe(II). In addition, some areas of the Ryugu pyrrhotite grains showed corroded structures with iridescence. Furthermore, assemblages of magnetite particles were also preferentially observed on small areas of the likely-dissolved pyrrhotite crystals in phyllosilicate matrices. These characteristic features in the Raman spectra and in corroded structures of Ryugu pyrrhotites record changes in the local environmental conditions via aqueous alteration. The corrosion of pyrrhotite crystals followed by the preferential formation of magnetite particles by asteroidal water is the likely product of dissolution of Fe(II) from the pyrrhotite surface and its oxidative precipitation in microchemical environments on the Ryugu parent body.