In order to determine the structural characterization of aluminosilicates in two types of fly ashes, two samples from Shanxi Province, China were selected for study. One was from a pulverized coal boiler (FA-1), and the other from a circulating fluidized bed boiler (FA-2). FA-1 had a much higher content of silicon dioxide (SiO₂) (70.30%) than FA-2(42.19%), but aluminum oxide (Al₂O₃) was higher in FA-2 (25.41%) than in FA-1 (17.04%). The characterizations were investigated using various methods including X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), magic angle spinning nuclear magnetic resonance (MAS–NMR) spectrometry, and X-ray photoelectron spectroscopy (XPS). The XRD analysis showed that FA-1 contained aluminosilicate glass, quartz and mullite, while FA-2 contained significant amounts of amorphous aluminosilicate, quartz and gypsum. The FTIR results showed an increased substitution of Al³⁺ for Si⁴⁺ as the band of asymmetric stretching vibrations Si–O(Si) (1100 cm⁻¹) moved to 1090 cm⁻¹ for FA-2, much lower than for FA-1(1097 cm⁻¹). Moreover, the sharpness of the bands in the 1250–1000 cm⁻¹ region for FA-2 indicates that the silicate structure of FA-2 was more ordered than for FA-1. It can be understood from the ²⁹Si MAS–NMR results that Q⁴(mAl) (Q⁴ are connected via 4 bridging O atoms to mAl) is the main structural type in FA-1 and FA-2, and that FA-2 contains more Al, which substitutes for Si in the Q⁴ structure. ²⁷Al MAS–NMR demonstrated that a combination of tetrahedral, pentahedral, and octahedral Al existed in FA-1 and FA-2. The Si 2p XPS spectra suggested that there were three forms of Si, including bridging Si (Si–O₂), non–bridging Si (Si–O), and SiO₂ gel. The content of Si–O₂ for FA-1 was 37.48% higher than Si–O (28.57%), while the content of Si–O₂ was 30.21% lower than Si–O (40.15%) for FA-2. The Al 2p XPS spectra showed that octahedral Al was the dominant form for FA-1 with a content of 40.25%, while the main phase was tetrahedral Al for FA-2 with a proportion of 37.36%, which corresponds well with the ²⁷Al MAS–NMR results.

Silicic, mafic and alkali intra-seam tonsteins have been known from SW China for a number of years. This paper reports on the geochemical compositions of coals and tonsteins from three seam sections of the Songzao Coalfield, SW China, and evaluates the geological factors responsible for the chemical characteristics of the coal seams, with emphasis on the influence from different types of volcanic ashes. The roof and floor samples of the Songzao coal seams mostly have high TiO₂ contents, consistent with a high TiO₂ content in the detrital sediment input from the source region, namely mafic basalts from the Kangdian Upland on the western margin of the coal basin. The coals from the Songzao Coalfield generally have high ash yields and are highly enriched in trace elements including Nb, Ta, Zr, Hf, rare earth elements (REE), Y, Hg and Se; some variation occurs among different seam sections due to input of geochemically different volcanic ash materials. The geochemistry of the Songzao coals has also been affected by the adjacent tonstein/K-bentonite bands. The relatively immobile elements that are enriched in the altered volcanic ashes also tend to be enriched in the adjacent coal plies, possibly due to leaching by groundwaters. The coals near the alkali tonstein bands in the Tonghua and Yuyang sections of the Songzao Coalfield are mostly high in Nb, Ta, Zr, Hf, Th, U, REE and Y. Coal samples overlying the mafic K-bentonite in the Tonghua section are high in V, Cr, Zn and Cu. The Datong coal, which has neither visible tonstein layers nor obvious volcanogenic minerals, has high TiO₂, V, Cr, Ni, Cu and Zn concentrations in the intervals between the coal plies affected by mafic and alkaline volcanic ashes. This is consistent with the suggestion that a common source material was supplied to the coal basin, derived from the erosion of mafic basaltic rocks of the Kangdian Upland. Although the Songzao coal is generally a high-sulfur coal, most of the chalcophile trace elements show either poor or negative correlations with total iron sulfide contents. The absence of traditional pyrite-metal associations may reflect wide variations in the concentrations of these elements in individual pyrite/marcasite components, or simply poor retention of these elements in the pyrite/marcasite of the relevant coals.

The clay mineralogy of pyroclastic Nb(Ta)-Zr(Hf)-REE-Ga mineralization in Late Permian coal-bearing strata from eastern Yunnan Province; southwest China was investigated in this study. Samples from XW and LK drill holes in this area were analyzed using XRD (X-ray diffraction) and SEM (scanning electronic microscope). Results show that clay minerals in the Nb-Zr-REE-Ga mineralized samples are composed of mixed layer illite/smectite (I/S); kaolinite and berthierine. I/S is the major component among the clay assemblages. The source volcanic ashes controlled the modes of occurrence of the clay minerals. Volcanic ash-originated kaolinite and berthierine occur as vermicular and angular particles, respectively. I/S is confined to the matrix and is derived from illitization of smectite which was derived from the original volcanic ashes. Other types of clay minerals including I/S and berthierine precipitated from hydrothermal solutions were found within plant cells; and coexisting with angular berthierine and vermicular kaolinite. Inferred from the fact that most of the I/S is R1 ordered with one case of the R3 I/S; the paleo-diagenetic temperature could be up to 180 °C but mostly 100–160 °C. The micro-crystalline quartz grains (<10 µm) closely associated with I/S were observed under SEM and were most likely the product of desiliconization during illitization of smectite.

Critical elements in coal and coal-bearing sequences (e.g., Li, Sc, V, Ga, Ge, Se, Y and rare earth elements, Zr, Nb, Au, Ag, platinum group elements, Re, and U) have attracted great attention because their concentrations in some cases may be comparable to those of conventional ore deposits. The enrichment of critical elements in coals, particularly those of Carboniferous-Permian and Cenozoic ages, have generally been attributed to within-plate (plume-related) volcanism and associated hydrothermal activity. However, Cretaceous coals are not commonly rich in critical elements, with the exception of some (e.g., Ge and U) in localised areas. This paper globally reviewed metalliferous coals from Siberia, the Russian Far East, Mongolia, South America, the United States and Mexico, Canada (Alberta and British Columbia), China, Africa, and Australasia (Victoria, Queensland, New South Wales, South Australia, Northern Territory, New Zealand, Nelson, West Coast, Canterbury, Otago, and Southland). The world-class Ge-U or Ge deposits in North China, Mongolia, and Siberia are the only commercially significant representatives of the Cretaceous metalliferous coals, which are related to bio-chemical reduction of oxidized meteoric, hydrothermal, or sea waters by organic matter of the peat bogs. The common Cretaceous coals worldwide are generally not rich in critical elements because intensive igneous activity led to extensive acidification of terrestrial and marine waters, which are responsible for the low coal metallogenesis during the Cretaceous period, especially the Early Cretaceous time.

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.