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.

This study presents recently collected data examining the organic petrology, palynology, mineralogy and geochemistry of the Gray Hawk coal bed. From the Early Pennsylvanian, Langsettian substage, Gray Hawk coal has been mined near the western edge of the eastern Kentucky portion of the Central Appalachian coalfield. While the coal is thin, rarely more than 0.5-m thick, it has a low-ash yield and a low-S content, making it an important local resource. The Gray Hawk coal palynology is dominated by Lycospora spp., and contains a diverse spectrum of small lycopods, tree ferns, small ferns, calamites, and gymnosperms. The maceral assemblages show an abundance of collotelinite, telinite, vitrodetrinite, fusinite, and semifusinite. Fecal pellet-derived macrinite, albeit with more compaction than is typically seen in younger coals, was observed in the Gray Hawk coal. The minerals in the coal are dominated by clay minerals (e.g., kaolinite, mixed-layer illite/smectite, illite), and to a lesser extent, pyrite, quartz, and iron III hydroxyl-sulfate, along with traces of chlorite, and in some cases, jarosite, szomolnokite, anatase, and calcite. The clay minerals are of authigenic and detrital origins. The occurrence of anatase as cell-fillings also indicates an authigenic origin. With the exception of Ge and As, which are slightly enriched in the coals, the concentrations of other trace elements are either close to or much lower than the averages for world hard coals. Arsenic and Hg are also enriched in the top bench of the coal and probably occur in pyrite. The elemental associations (e.g., Al₂O₃/TiO₂, Cr/Th-Sc/Th) indicate a sediment-source region with intermediate and felsic compositions. Rare metals, including Ga, rare earth elements and Ge, are highly enriched in the coal ashes, and the Gray Hawk coals have a great potential for industrial use of these metals. The rare earth elements in the samples are weakly fractionated or are characterized by heavy-REE enrichment, indicating an input of natural waters or probably epithermal solutions.

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.

The increasing demand for rare earth elements (REEs), which is associated with their economic importance and the supply risk, has motivated the research for alternative secondary sources of these elements. Coal and coal combustion ash have been pointed out as promising REE raw materials. This research seeks to understand REE fractionation, from feed coals to ashes, considering seasonal variations, and to assess the trends within the ash fractions that can be used for further beneficiation processes. Colombian commercial feed coals, combustion ashes, and their respective fractions were sampled from a Portuguese power plant and were characterized via petrographical, mineralogical, and chemical analyses. The total REE concentrations in the feed coals studied range between 6.97 and 23.15 ppm, while, in the ashes, they vary from 159.9 to 266.6 ppm. Fly ash (FA) from electrostatic precipitator (ESP) presented higher concentrations than the bottom (BA) and economizer (ECO) ashes. Furthermore, REEs and the LREE/HREE ratio increased slightly towards the back rows of the ESP. In the feed coals, the REEs are significantly correlated with ash, and they occur in micrometric phosphate minerals intermixed with clays. In the ashes, the REEs were mostly detected in micrometric particles, with P and Al-Si as the major components. The results from the fractioned samples show that the REEs were enriched in the fine (<25 µm) and nonmagnetic fractions of the ESP FA. A single trial combining sieving and magnetic separation enabled the attainment of a REE recovery of 53%, and a final enrichment factor of 1.25. Coal combustion ashes and their respective size fractions are promising REE raw materials; however, the REE oxide concentrations are below the economical cutoff of 1000 ppm.

High amounts of coal combustion products, such as fly ash and bottom ash, are generated every year; however, only 64% are used, which means that a significant part is landfilled despite containing valuable materials such as ferrospheres, which may be used as catalysts, substituting critical raw materials (e.g., platinoids). In commercial coals, pyrite contents are reduced as a pre-combustion S-emissions control measure, so low amounts of ferrospheres are expected in the respective ashes. However, given the large amounts of ash being generated from these coals, it may provide a reliable source of catalysts, with ferrospheres being easily recovered via magnetic separation. Several studies have been conducted regarding these morphotypes; however, there is a lack of investigation considering the ash derived from highly beneficiated coals and the variations with location and time. In this study, bottom ash, economizer grits, and fly ash samples from a Portuguese power plant burning Colombian commercial coal were fractionated using ferrite (Fe-MC fraction) and Nd (Nd-MC fraction) magnets, and a multi-technique approach was used to assess their properties (magnetic parameters, particle size distribution, mineralogy, particle morphology, microtexture, and chemical composition). The Fe-MC presented higher Fe concentrations (up to 44 wt.% Fe₂O₄) than the Nd-MC (up to 7 wt.% Fe₂O₄). Once it was a sequential process, Nd magnets essentially collected Fe-bearing aluminosilicate glass, and Fe-bearing minerals were residual when compared to the Fe-MC, where magnetite, magnesioferrite, hematite, and maghemite accounted for up to 30 wt.%. Among the Fe-MC, the sample collected from electrostatic precipitator fly ash (ESP FA), despite having a lower yield, presented higher Fe concentrations than the ones from bottom ash and economizer grits, which was related to the mode of occurrence of Fe-bearing phases: in the Fe-MC from ESP FA, discrete ferrospheres predominated, while in the remaining Fe-bearing phases, they were often embedded in aluminosilicate glass. All Fe-MC samples showed an increase of Fe-substituting elements (e.g., Mn and Ni) and their concentration tended to increase with decreasing particle size along with Fe. The integrated study of cross-sections enabled the identification of oxidation rims, martitization aspects, and the co-existence of hematite and magnesioferrite.