Formation of N–С–О–Н molecules and complexes in the basalt–basaltic andesite melts at 1.5 Gpa and 1400°C in the presence of liquid iron alloys

Abstract

The contents and speciation of nitrogen, carbon, and hydrogen were determined in basalt–basaltic andesite melts in equilibrium with liquid Fe alloys at 1.5 Gpa, 1400°C, and oxygen fugacity (fO2) 1.4–1.9 log units below that of the Fe–FeO buffer (ΔlogfO2(IW) =–1.4 …–1.9). Experiments were carried out on a piston- cylinder type apparatus using welded Pt capsules in the presence of excess С (graphite). Starting mixture consisted of natural ferrobasaltic glass and silicon nitride (Si3N4) as nitrogen source in the system. Experimental quench products representing glasses with spherical inclusions of iron alloy were analyzed using electron microprobe, Raman, and IR spectroscopy. With increase of Si3N4 in the starting mixture and, respectively, decrease of fO2, silicate melt forming during experiments became depleted in FeO and enriched in SiO2. It was established that the nitrogen content in the glasses increases from 0.13 to 0.44 wt % with decrease of ΔlogfO2(IW) from–1.4 to–1.9, whereas C content in the first approximation remains constant within 1.18–1.13 wt %, while the total water content (ОН– + Н2О) determined by IR spectroscopy decreases from 4.91 to 1.20 wt %. The N (0.13–0.48 wt %) and C (0.75–2.26 wt %) contents determined in the Fe alloy show no clear correlation with fO2. The IR and Raman spectroscopic study of the glasses indicates the formation of molecules and complexes with bonds N–H (NH3, NH2−, NH2+, NH4+), Н–О (Н2О, OH–), С–Н (СН4) as well as N2 and Н2 molecules in silicate melts. IR spectra also reveal the presence of complexes with С=О, С–N bonds and СО2 molecules. Obtained data are compared with results of previous studies on the solubility and speciation of N, С, and Н in the model FeO–Na2O–SiO2–Al2O3 melts in equilibrium with liquid iron alloys at 1.5 GPa (1400°C) and 4 GPa (1550°C) (Kadik et al., 2011, 2015).