Application of IR and Raman spectroscopy for the determination of the role of oxygen fugacity in the formation of N–С–О–Н molecules and complexes in the iron-bearing silicate melts at high pressures

Large-scale melting of the Earth’s early mantle under the effect of global impact processes was accompanied by the generation of volatiles, which concentration was mainly controlled by the interaction of main N, C, O, and H gas-forming elements with silicate and metallic melts at low oxygen fugacity (fO₂), which predominated during metallic segregation and self-oxidation of magma ocean. The paper considers the application of Raman and IR (infrared) Fourier spectroscopy for revealing the mechanisms of simultaneous dissolution and relative contents of N, C, O, and H in glasses, which represent the quench products of reduced model FeO–Na₂O–Al₂O₃–SiO₂ melts after experiments at 4 GPa, 1550°C, and fO₂ 1.5–3 orders of magnitude below the oxygen fugacity of the iron—wustite buffer equilibrium (fO₂(IW)). Such fO₂ values correspond to those inferred for the origin and evolution of magma ocean. It was established that the silicate melt contains complexes with N–H bonds (NH₃, NH₂⁺, NH₂^-), N₂, H₂, and CH₄ molecules, as well as oxidized hydrogen species (OH^– hydroxyl and molecular water H₂O). Spectral characteristics of the glasses indicate significant influence of fO₂ on the N–C–O–H proportion in the melt. They are expressed in a sharp decrease of NH₂⁺, NH₂^-(O–NH₂), OH^–, H₂O, and CH₄ and simultaneous increase of NH₂^-(≡Si–NH₂) and NH₃ with decreasing fO₂. As a result, NH₃ molecules become the dominant nitrogen compounds among N–C–H components in the melt at fO₂ two orders of magnitude below fO₂(IW), whereas molecular СН₄ prevails at higher fO₂. The noteworthy feature of the redox reactions in the melt is stability of the ОН^– groups and molecular water, in spite of the sufficiently low fO₂. Our study shows that the composition of reduced magmatic gases transferred to the planet surface has been significantly modified under conditions of self-oxidation of mantle and magma ocean.