Clay Minerals in Carboniferous Ash-Rich Coals of Kazakhstan: Roles in Geochemical Signatures and Elemental Distribution Patterns

Clay minerals in coal play a key role in controlling mineralogical composition, geochemical signatures, and the industrial behavior of coal and its combustion residues. This study investigates the occurrence, provenance, and potential applications of clay minerals in Carboniferous ash-rich coals from the Bogatyr, Lenin, and Saradyr coal mines in northeastern Kazakhstan. A total of 60 coal samples were analyzed using XRD, SEM–EDS/BSE, XRF, and ICP-OES following acid leaching. Based on ash yield, 52 samples were classified as coal (50% ash). Mineralogical assemblages show clear variability among the studied mines. Saradyr samples are strongly quartz-dominated with lower clay proportions, Bogatyr samples exhibit highly heterogeneous quartz–clay–mica assemblages, whereas Lenin samples are relatively more clay-rich and dominated by kaolinite and illite-group minerals. Across all samples, kaolinite is the dominant clay mineral (16.6–46 wt.%), occurring mainly as authigenic pore- and cell-filling aggregates. Minor phases include illite–muscovite (7.1–29.9 wt.%), illite–smectite (up to 7.6 wt.% in Bogatyr), and smectite–montmorillonite (0.4–0.7 wt.%). Clay minerals occur as discrete particles, coatings, and pore fillings, contributing to ash formation; however, their correlation with ash yield is weak (R = 0.03–0.05), reflecting heterogeneous mineral inputs and diagenetic overprinting. All geochemical data are reported on a high-temperature coal ash (HTA) basis (815 °C). Geochemical indices (CIA, CIW, CIX) and Al2O3/TiO2 ratios (1.8–17.4) indicate variable provenance and moderate to high weathering intensity, reflecting mixed mafic to intermediate source rocks. A total of 23 trace elements were identified. Au occurs at trace levels (up to 0.02 ppm), while selected rare earth elements (REE: Ce, Dy, Eu, La, Nd, Sm, Y, Yb) average 0.2–0.3 ppm, indicating negligible economic recovery potential. REEs show a strong positive correlation with clay minerals (r = 0.93), indicating adsorption and minor structural incorporation. In contrast, Au correlates with As, V, Zn, Cu, Ni, and Nb, suggesting sulfide association. HTA is enriched in SiO2–Al2O3 phases dominated by kaolinite and quartz, indicating strong potential for cement, geopolymer, ceramic, and zeolite applications.