Raman spectroscopy study of C-O-H-N speciation in reduced basaltic glasses: Implications for reduced planetary mantles

To better understand the solution of volatile species in a reduced magma ocean, we identify via Raman spectroscopy the nature of C-O-H-N volatile species dissolved in a series of reduced basaltic glasses. The oxygen fugacity (f O2) during synthesis varied from highly reduced at two log units below the iron-wustite buffer (IW-2.1) to moderately reduced (IW-0.4), spanning much of the magmatic f O2 conditions during late stages of terrestrial accretion. Raman vibrational modes for H2, NH2 – , NH3, CH4, CO, CN– , N2, and OH– species are inferred from band assignments in all reduced glasses. The integrated area of Raman bands assigned to N2, CH4, NH3 and H2 vibrations in glasses increases with increasing molar volume of the melt, whereas that of CO decreases. Additionally, with increasing f O2, CO band areas increase while those of N2 decrease, suggesting that the solubility of these neutral molecules is not solely determined by the melt molar volume under reduced conditions. Coexisting with these neutral molecules, other species as CN– , NH2 – and OH– are chemically bonded within the silicate network. The observations indicate that, under reduced conditions, (1) H2, NH2 – , NH3, CH4, CO, CN– , N2, and OH– species coexist in silicate glasses representative of silicate liquids in a magma ocean (2) their relative abundances dissolved in a magma ocean depend on melt composition, f O2 and the availability of H and, (3) metal-silicate partitioning or degassing reactions of those magmatic volatile species must involve changes in melt and vapor speciation, which in turn may influence isotopic fractionation.CD and MH acknowledge support from the National Science Foundation grant AST1344133. SDJ acknowledges support from NSF EAR-1853521 and the David and Lucile Packard Foundation