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This paper reports the mineralogy and geochemistry of the Late Permian C1 Coal from Bole and Laibin mines in eastern Yunnan, Southwestern China (C1 Coal in Laibin mine is composed of three layers termed B1, B2, and B3). The coals are characterized by medium-high ash yields and very low sulfur contents. Compared with average values of trace element concentrations in hard coals worldwide, the Bole and Laibin coals are enriched in V, Co, Cu, Zn, and Se, which were mainly derived from the sediment-source region of the Kangdian Upland. Major minerals in the coal samples and roof and floor strata include quartz, interstratified berthierine/chamosite (B/C), as well as kaolinite, mixed layer illite/smectite, calcite, pyrite, and anatase. Unlike a pure chamosite, the 7 Å peak of interstratified B/C is sharp and narrow, while the 14 Å peak is broad and weak, or absent in some coal samples. Interstratified B/C was largely precipitated from low-temperature Fe-rich and Mg-rich hydrothermal fluids or, in some cases, is an alteration product of kaolinite. Secondary phases of quartz, calcite, pyrite, kaolinite, chalcopyrite, gypsum, and REE-phosphates in the coal samples are the dominant authigenic minerals formed at syngenetic and early diagenetic stages. Four intra-seam partings in C1 Coal, B1, and B3 layers are identified as tonsteins derived from felsic volcanic ashes. These tonsteins consist mainly of cryptocrystalline kaolinite with graupen and vermicular textures, and minor amounts of high-temperature quartz, zircon, apatite, monazite, and anatase. The floor of the C1 Coal in the Bole mine is a tuffaceous claystone and consists of altered high-Ti basalt volcaniclastics, characterized by high concentrations of Zr, Nb, V, Co, Cu, and Zn, low Al2O3/TiO2 ratio (~4.62), high Ti/Y ratio (~900), enrichment of middle rare earth elements, and positive Eu anomalies. [ABSTRACT FROM AUTHOR]