New data, including Raman spectroscopy, characterize unusual mineral assemblages from rocks of the Naylga and Khamaryn–Khyral–Khiid combustion metamorphic complexes in Mongolia. Several samples of melilite–nepheline paralava and other thermally altered (metamorphosed) sedimentary rocks contain troilite (FeS), metallic iron Fe0, kamacite α-(Fe,Ni) or Ni-bearing Fe0, taenite γ-(Fe,Ni) or Ni-rich Fe0, barringerite or allabogdanite Fe2P, schreibersite Fe3P, steadite Fe4P = eutectic α-Fe + Fe3P, wüstite FeO, and cohenite Fe3C. The paralava matrix includes a fragment composed of magnesiowüstite–ferropericlase (FeO–MgO solid solution), as well as of spinel (Mg,Fe)Al2O4 and forsterite. The highest-temperature mineral assemblage belongs to a xenolithic remnant, possibly Fe-rich sinter, which is molten ash left after underground combustion of coal seams. The crystallization temperatures of the observed iron phases were estimated using phase diagrams for the respective systems: Fe–S for iron sulfides and Fe–P ± C for iron phosphides. Iron monosulfides (high-temperature pyrrhotite) with inclusions of Fe0 underwent solid-state conversion into troilite at 140 °C. Iron phosphides in inclusions from the early growth zone of anorthite–bytownite in melilite–nepheline paralava crystallized from <1370 to 1165 °C (Fe2P), 1165–1048 °C (Fe3P), and <1048 °C (Fe4P). Phase relations in zoned spherules consisting of troilite +Fe0 (or kamacite + taenite) +Fe3P ± (Fe3C, Fe4P) reveal the potential presence of a homogeneous Fe–S–P–C melt at T~1350 °C, which separated into two immiscible melts in the 1350–1250 °C range; namely, a dense Fe–P–C melt in the core and a less dense Fe–S melt in the rim. The melts evolved in accordance with cooling paths in the Fe–S and Fe–P–C phase diagrams. Cohenite and schreibersite in the spherules crystallized between 988 °C and 959 °C. The crystallization temperatures of minerals were used to reconstruct redox patterns with respect to the CCO, IW, IM, and MW buffer equilibria during melting of marly limestone and subsequent crystallization and cooling of melilite–nepheline paralava melts. The origin of the studied CM rocks was explained in a model implying thermal alteration of low-permeable overburden domains in reducing conditions during wild subsurface coal fires, while heating was transferred conductively from adjacent parts of ignited coal seams. The fluid (gas) regime in the zones of combustion was controlled by the CCO buffer at excess atomic carbon. Paralava melts exposed to high-temperature extremely reducing conditions contained droplets of immiscible Fe–S–P–C, Fe–S, Fe–P, and Fe–P–C melts, which then crystallized into reduced mineral assemblages.
