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Industrial applications of coal rely on understanding its macromolecular structure, which is primarily controlled by coal type and rank. The present study assessed five (5) samples from different collieries extracting coal from the No. 4 Seam of the Highveld Coalfield and their float products, produced at relative densities (RD) of 1.7 and 1.9 g/cm3. The aim was to assess changes in maceral composition and coal quality following the density fractionation, and to use Raman Spectroscopy to compare differences in macromolecular structures between the parent samples and the float products. Raman parameters were also determined for specific macerals, i.e., semifusinite and collotelinite. Mean random vitrinite reflectance (%RoV) values for the studied coals range between 0.57 and 0.60% (medium rank D/C bituminous) and the parent coals are inertinite-rich (70.3 to 88.7 vol% mmf), enriched in semifusinite and inertodetrinite. Following density fractionation, reactive macerals (a combination of liptinite, vitrinite, and reactive semifusinite) are enriched in the float products (designated by "F"), specifically in the products obtained at the 1.7 RD. In comparison, the proportion of inert macerals is higher in the F1.9 samples. These differences in maceral composition are reflected in the Raman spectra and parameters. Although the G and D1 bands for the parent coals and F1.9 samples are similar, these bands are narrower than for the F1.7 samples, indicative of greater aromaticity. The G FWHM values for the F1.9 samples are comparable to those for the parent coal samples, and lower than for the F1.7 samples. This reflects larger differences in maceral composition between the parent coals and the F1.7 samples. In contrast, the D1 FWHM values for the float products, particularly the F1.7 samples, are slightly higher than the parent coals, reflecting a disordered aromatic character mainly related to the presence of aliphatic chains. The Raman spectra for the F1.7 samples are more like that for collotelinite. In contrast, the Raman spectra and parameters (G and D1 FWHM) for the F1.9 samples are more comparable to semifusinite. Thus, the increased aliphaticity for the F1.7 samples is attributed to the relative enrichment of reactive macerals, whereas higher aromaticity for the F1.9 samples reflects a larger proportion of inert macerals. Raman spectroscopy expanded on the petrographic data by interrogating the macromolecular structure of the isorank Highveld coals and their float products. This may assist in predicting the behaviour of the coals during industrial applications (i.e., liquefaction, gasification, combustion, and carbon fibre production). [Display omitted] [ABSTRACT FROM AUTHOR]

The emplacement of igneous intrusions into coal alters both the organic and inorganic components, and may result in the addition of specific components, including rare earth elements (REEs), into the country rock. Previous studies on the intruded coals of the Main Karoo Basin (South Africa) have mainly focused on understanding changes to their organic fraction despite the likelihood that the inorganic composition is also affected, as demonstrated by others studying intruded coals elsewhere in the world. This study reports on the effects of a 0.4 m thick dolerite dyke on the mineralogy and geochemistry of Witbank coals, South Africa. Coal samples were collected at 0.25 m intervals on both sides of the dyke (west and east); in addition to the intruded coals, an unaltered coal from the same seam and a sample of the dolerite were included. The samples were assessed using petrography, X-Ray Diffraction, X-Ray Fluorescence, Scanning Electron Microscopy, and Inductively Coupled Plasma Mass Spectrometry following sequential leaching, focusing on REEs for the latter analysis. Inertinite is the main maceral group in the coal samples; as a result, the impact of the intrusion on the organic fraction is compared using mean random total reflectance (%RoTmr). Total reflectance increases from 1.65 %RoTmr (for the unaltered coal) to 4.17 %RoTmr closer to the dyke on the western side. In contrast, the eastern side reports lower values (max. 1.94 %RoTmr). Similar to reflectance, dolomite is higher in samples from the western side of the dyke. Dolomite is also found in the unaltered coal (4 wt%) and the dolerite sample (15 wt%). Syngenetic dolomite and a weak positive Gd anomaly for the unaltered coal (ΣREE = 83.7 μg/g) suggest the presence of acidic groundwaters during peatification. Subsequently, the coals were also affected by hydrothermal activity, related to the intrusion of the dolerite dyke. For the intruded coals, dolomite (fracture-infilling) and ΣREEs are higher on the western side, at a maximum of 24 wt% and 153.0 μg/g, respectively. Carbonate associated REEs are higher for the intruded coals than the total for the dolerite (ΣREE = 23.3 μg/g). This reflects the incompatibility of REEs with early-formed minerals in the dolerite, concentrating them in the residual melt. Increased reflectance and dolomite (and associated REEs) in coals from the western side suggest pronounced hydrothermal activity, related to the availability of accommodation space (i.e., fractures). [Display omitted] • Two sets of intruded Witbank coals were studied. • Dolomite is a significant epigenetic phase. • A high proportion of REEs is associated with carbonates. • Reflectance, dolomite, and ΣREEs are higher in the west of dyke. [ABSTRACT FROM AUTHOR]

Highlights • Inertinite- and vitrinite-rich sub-samples were prepared using density separation. • The coal samples were compared using δ15N and δ13C and nitrogen functionalities. • Coal formation pathways were inferred for the dominant macerals of each sample. • Low 14N and high N-quaternary for the vitrinite-rich imply bacterial degradation. • Higher 14N and N-pyrrolic values for the inertinite-rich sample suggest charring. Abstract Fires are likely to have been central to the formation of certain inertinite macerals in South African coals. To investigate this hypothesis, a Permian, medium rank C bituminous Witbank coal (No. 4 Seam Upper) was density fractionated to yield an inertinite-rich and a vitrinite-rich sample, and assessed using stable nitrogen and carbon (δ15N and δ13C) isotopes in conjunction with nitrogen functionalities. The parent coal comprises of 41.6 vol% vitrinite and 48.5 vol% inertinite. The vitrinite-rich sample is dominated by collotelinite and collodetrinite (81 vol% vitrinite), and the inertinite-rich sample by fusinite, semifusinite, and inertodetrinite (63 vol% inertinite). The δ15N and δ13C values and nitrogen functionalities were used to constrain early coal formation pathways for the dominant macerals in the density fractionated samples. The vitrinite-rich sample has a lower δ13C relative to the inertinite-rich counterpart. However, the inertinite-rich sample has the lower δ15N value, along with a lower concentration of N-quaternary and higher N-pyrrolic compounds. Because these samples are of the same coal maturity, and the major macerals were derived from similar precursors, differences in δ15N and δ13C and nitrogen functionalities reflect differences in coal formation pathways. Degradation of 13C-rich cellulose in wood through either charring or bacterial activity leads to lower δ13C values. The lower 14N content for the vitrinite-rich sample along with higher N-quaternary and N-pyridinic suggests cellulose degradation driven by bacterial activity. In contrast, the higher 14N coupled with higher N-pyrrolic and N-oxide complexes for the inertinite-rich sample, suggests fusinite and semifusinite were formed through charring. Inertodetrinite is attributed to the disintegration of the charred matter. [ABSTRACT FROM AUTHOR]

In this study, carbon-13 cross-polarization magic-angle-spinning solid-state nuclear magnetic resonance ( 13 C CP-MAS SS NMR) was undertaken on a parent coal sample and its density-fractionated derivatives, an inertinite-rich and a vitrinite-rich sample, obtained from the Witbank Coalfield of South Africa (medium rank C bituminous coal). The formation of inertinite macerals has been extensively researched and the conclusions remain largely controversial. However, most research has been confined to northern hemisphere coals, which are typically dominated by vitrinite. South African coals are widely known for their high inertinite content. Earlier workers have ascribed the inertinite macerals, in their diversity, to aerial oxidation. However, this oxidation-only pathway fails to recognize that inertinite macerals can form through other processes such as charring of plant matter. Microscopically, charred matter possesses anatomical structures that closely resembles those observed in inertinite macerals, with lignin and/or cell walls largely preserved, perhaps mechanically fragmented or compressed in some instances. Based on the NMR structural parameters, the average aromatic cluster size in the inertinite-rich sample (petrographically dominated by fusinite, semifusinite of varying reflectance, and inertodetrinite) corresponds to monocyclic, 6-aromatic carbon rings. In the vitrinite-rich sample of the same coal, the cluster sizes are larger, corresponding to multi-ring aromatic hydrocarbons. The 6-carbon rings in the inertinite-rich sample are interpreted to correspond to guaiacol and syringol, the principal products of low-temperature (below 400 °C) lignin pyrolysis. Since charring depletes cellulose and moisture, fire-affected plant matter is interpreted to have a lower compaction potential than vitrinite-forming material, sustaining 6-aromatic carbon ring isolation in the former. Lignin-derived aromatic rings in compactable plant matter merge to form the multi-ring clusters present in the collotelinite- and collodetrinite-rich sample of the same coal. [ABSTRACT FROM AUTHOR]

In this study, δ13C, δ15N, and nitrogen functional forms were used to evaluate the effects of contact metamorphism on inertinite-rich Main Karoo Basin coals (South Africa). Eighteen samples were collected at 0.25 m intervals from the western and eastern sides of a ∼ 2.6 m thick dolerite dyke emplaced into the No. 2 Seam; an unaltered coal from the same seam was included as a control (Witbank Coalfield). Inertinite (semifusinite and inertodetrinite) dominated the organic composition of the samples. δ13C and δ15N for the unaltered coal were − 21.1‰ VPDB and 1.5‰ Air, respectively. For the intruded coals from the western side, δ13C ranged between −22.4 and −21.4‰ VPDB, and δ15N between 1.2 and 2.6‰ Air. The δ13C for samples from the eastern side ranged between −21.8 and −20.7‰ VPDB, and between 1.8 and 3.0‰ Air for δ15N. Differences in δ15N between the unaltered and the intruded coals were generally more significant than in δ13C, especially for samples from the eastern side. The positive shifts in δ15N may reflect reactions between organic nitrogen in coal and mobile nitrogen transported by hydrothermal fluids. The absence of a relationship between δ15N and distance from the dyke, may reflect secondary, localized contact metamorphism due to hydrothermal fluid migration within the intruded seam. The circulation of a fluid transporting 15N-rich moieties, apparently more active on the eastern side, was supported by the higher ash yields, δ15N, and N total /C organic ratios. The correlation between N total /C organic and ash yields suggests deposition of NH 4 + − bearing inorganic components preferentially into the eastern side. Similar to the unaltered coal (N-5 = 47.24 at.%), N-pyrrolic was the dominant nitrogen functional form of the intruded coals, reflecting the developmental pathways for the inertinite macerals as opposed to the contact metamorphism. The low proportion of graphitic (quaternary) nitrogen, irrespective of sample distance from the dyke, suggests metamorphic temperatures lower than 900 °C. [ABSTRACT FROM AUTHOR]

Petrological and mineralogical features are key for inferring palaeoenvironmental and sedimentary conditions of coal-bearing sediments. Following the logging of a borehole core, this study reports on the organic petrology and mineralogy of the A and B Seams, Ermelo Coalfield, Main Karoo Basin (MKB), South Africa. Seventeen coal samples collected from the core, differentiated based on changes in lithotypes, were assessed using detailed petrography (macerals, microlithotypes, and mean random vitrinite reflectance), quality analyses (proximate, elemental, and gross calorific value), and mineralogy in order to deduce depositional environments for the Ermelo coals. The lithologies present in the core were typical of the MKB, and the coals were inertinite- and mineral matter-rich, apart from samples occurring at the base of the seams. The latter samples also had a higher proportion of structured inertinite macerals (fusinite and semifusinite) and lower ash yields. The rest of the samples had higher inertodetrinite contents, occurring in association with detrital quartz and kaolinite, resulting in higher ash yields. The formation of each coal seam thus commenced with the prevailing conditions conducive to the preservation of structured macerals and concluded with the accumulation of predominantly inertodetrinite. Select samples from the B Seam also had durite, an association of inertodetrinite and liptinite (including alginite). The co-occurrence of inertodetrinite and the detrital minerals alongside alginite suggests two depositional episodes. The first episode relates to the formation of primary inertinite macerals through charring, followed by fragmentation and redeposition as inertodetrinite. This latter process likely also reflects seasonal flooding, resulting in fluctuating water levels within the palaeomire. The second episode was quieter, occurring in deeper waters, and conducive for the growth of algae. An allochthonous origin is thus proposed for inertodetrinite and the associated detrital minerals, whereas alginite deposition was autochthonous. The cyclical upward-fining and upward-coarsening facies of the MKB were observed in the core, indicative of fluvial and deltaic palaeoenvironments, respectively. The fluvial facies were generally associated with the occurrence of structured vitrinite and inertinite macerals, suggesting in-situ formation, and mostly occur at the base of the coal seams. In contrast, the inertodetrinite-rich samples appear to be related to the overlying deltaic deposits. • An Ermelo core intersecting the A and B Seams is described. • Inertinite is common in the coals, though vitrinite is higher at the base of the seams. • In some B Seam samples, alginite occurs with inertodetrinite reflecting autochthonous and allochthonous deposition. • Structured macerals are associated with fluvial facies and inertodetrinite with deltaic facies. [ABSTRACT FROM AUTHOR]

The response of inertinite-rich Witbank coals (South Africa) to rapid heating was evaluated using petrography, selected Nuclear Magnetic Resonance (NMR) and X-Ray Diffraction (XRD) structural parameters. A total of thirteen (13) coal samples were collected from the No. 2 Seam; a set of six (6) samples from the western and the eastern sides of a ~ 0.4 m thick dolerite dyke emplaced into the coal seam at 0.25 m intervals. An unaltered coal (Un-C; the 13th sample), collected away from the dyke but within the same seam at the mine, was included for comparison. All 13 coal samples were dominated by inertinite. Semifusinite was most abundant in the samples from the western side of the dyke, whereas the proportion of inertodetrinite was highest in samples from the eastern side. Due to very low vitrinite contents, mean random total reflectance (%RoTmr) was used to compare the maturity of the inertinite-rich coals. A decrease in volatile matter was correlated with an increase in mean random total reflectance (%RoTmr; measured on semifusinite, inertodetrinite, and vitrinite), the latter used as a potential maturity indicator for the thermally altered inertinite-rich coals. Mean random total reflectance rose from a background value of 1.52%RoTmr (for Un-C) to 2.83%RoTmr for the coal sample at the western coal-dyke contact (0.0 m). The corresponding reflectance values for the thermally altered coals from the eastern side were less consistent, decreasing closest to the dyke (1.93%RoTmr for the sample at 0.0 m); this trend is also reflected in the NMR and XRD parameters. Eight (8) samples were selected for the NMR analysis, representative of the maceral composition and maturities of the coals investigated. For Un-C, the fraction of aromatic carbons (fa) was 0.88 (average number of carbons per aromatic cluster (C) = 17), and the interplanar spacing (d002) was 3.48 Å (with a crystallite height of 22.09 Å). For the thermally altered coals from the western side, fa decreased from 0.96 at the coal-dyke contact (C = 26 for sample at 0.0 m) to 0.92 for the sample at 1.25 m from the dyke (C = 20). For samples from the eastern side, fa increased from 0.91 (C = 19 for the sample at 0.25 m) to 0.93 (C = 23 for sample at 0.5 m), before decreasing to 0.89 further from the dyke (C = 18 for sample at 1.25 m). In general, the d002 values for the thermally altered coal samples were larger than for graphite. Similarly, only marginal increases in crystallite heights were observed. Although the dyke induced coal maturation and the resultant increase in fa , the overall lack of graphitic order in the thermally altered coals was ascribed to the limited thermal energy provided by the relatively thin dyke; increased heat input would be required to effect significant structural changes in the inertinite-rich coals. Differences between the two sets of thermally altered coal samples were attributed to the emplacement dynamics of the igneous intrusion, which require further investigation. [ABSTRACT FROM AUTHOR]

• Nine articles are reviewed for the VSI of the 38th Annual Conference of The Society for Organic Petrology [ABSTRACT FROM AUTHOR]

The increased global demand for rare earth elements (REEs) from unconventional sources has led to increased interest and research in coal deposits. South Africa has extensive coal resources, but understanding of the concentration, mode of occurrence, and distribution of REEs in the coals and associated sediments is limited. This study aims to assess selected coal samples obtained from an exploration project underway in the Waterberg Coalfield (South Africa) to determine the concentration and mode of occurrence of REEs, and to gain insight into the behaviour of REEs during density fractionation. Density fractionation of coal is considered a pre-concentration method prior to REE extraction. Samples were selected from zones 8, 7, 4, and 3, spanning the Grootegeluk and Vryheid Formations of the Waterberg Coalfield. Density fractionation was conducted at relative densities (RD) of 1.3 to 1.8, providing float (F) and sink (S) products. Five parent and thirty density-fractionated coal samples were characterized using proximate analysis, petrography, X-ray diffraction (XRD), and the concentration of REEs determined using Inductively Coupled Plasma- Mass Spectrometry (ICP-MS) (after microwave digestion). The samples are classified as medium-rank C bituminous coals with variable maceral composition. The dominant minerals are kaolinite and quartz, occurring as both syngenetic and epigenetic phases. The total REY (REEs + yttrium) concentrations range from 45.1 to 389.2 ppm, higher than for world coals (except sample 8H F1.30, REY = 45.1 ppm), and generally higher than the average for Chinese coals. Float products obtained at 1.40 to 1.80 RD show greater variation of light REY (LREY) compared to medium REY (MREY) and heavy REY (HREY), whereas float fractions at 1.30 and sink fractions at 1.80 RD show no distinct enrichment patterns. Although the results suggest a relationship between the concentration of LREY with float fractions obtained between 1.40 and 1.80 RD, pre-concentration using density fractionation generally shows limited benefits for these coals. Ashing of the coals may be more effective in concentrating the REEs and further investigations are therefore required. • The REY concentrations range from 45.1 to 389.2 ppm, comparable to or higher than that of world coal average values. • Density fractionated 1.4–1.8 float products show a greater variation of light REY (LREY) compared to medium REY (MREY) and heavy REY (HREY). • Pre-concentration by density fractionation may not be the best REY concentration process for these Waterberg coal samples. [ABSTRACT FROM AUTHOR]

In this contribution, we report the palynology, organic petrography and carbon isotopes for the #16 Seam in the Lower Cretaceous Yimin Formation of the Hailar Basin, Inner Mongolia, China. Eighteen palynological samples were collected from the coal seam as well as from intraseam partings and the immediate roof. Microfloras comprise a diverse assemblage of ferns, conifers, horsetails, lycopsids, bryophytes, ginkgoes and cycads. Conifer pollen is common, especially representative of Pinaceae (Pinuspollenites) as well as Cheirolepidiaceae (Classopollis) and Araucariaceae (Araucariacites, Chasmatosporite s); however, this material is interpreted as mostly derived from an upland source rather than from the mire-forming vegetation. An overrepresentation of conifer pollen may explain the relatively poor abundance and diversity of ginkgo and cycad pollen, compared to what is found in the macrofossil record. The palynological assemblage found in Seam #16 indicates a Barremian to Aptian age. Maceral composition, ash yields, and δ13C org signature of the coal suggest peat accumulation was controlled by a rising water table from flooding of the mire, coupled with significant ground (peat) fires and/or surface wildfires. These conditions resulted in high levels of detrital mineral matter and charcoal input, the latter represented by inertodetrinite in the coals. The top of the coal seam is characterised by a higher ash yield, lower δ13C org values and increased sphagnacean spores, which suggest the gradual drowning of the palaeomire. Although angiosperms were present in the Hailar Basin during the time that Seam #16 was accumulating, they are absent from the pollen found in this study. This may indicate that they were not yet adapted to the extreme conditions of the mire (e.g., acidity, anoxia), and unable to compete with the established mire vegetation. • Abundant fossil charcoal in the Seam #16 shows fire as an important part of palaeomire ecology. • Ash yields and δ13C org values indicate that flooding terminated the palaeomire. • Some pollen was likely derived from upland conifer forests and transported into the mire. • The absence of angiosperms reflects the harsh, palaeomire conditions. [ABSTRACT FROM AUTHOR]

• Petrology, δ13C and gypsum of coal corroborate alternating dry and wet periods. • The fine-scale variability in the δ13C signature was controlled by plant type. • δ13C values positively correlated with angiosperm/gymnosperm and % gypsum. • A high δ13C spike caps each of the four longer-term cycles of peat deposition. • The atmosphere had a significant influence on the peat formation in the basin. Coal contains detailed long-term records of contemporaneous environment, climate, and subsequent diagenetic processes. Stable isotopes of carbon, petrological, palynological, and mineralogical analyses were carried out on a 28 m thick low-rank Miocene coal seam from the Mile Basin, Yunnan Province, China for the purpose of deciphering the palaeoclimate and sedimentary conditions during peat deposition. The coal is characterized by both pale and dark lithotypes. Palynological analyses show that both lithotypes are dominated by angiosperms, which is interpreted to indicate a moderately warm climate. The absence of Fagus and Taxodiaceae pollen suggests that there may have been dry periods during peat accumulation; in general, both Fagus and Taxodiaceae require a constant wet environment in order to proliferate. Organic petrography, δ13C, and gypsum concentrations corroborate that there were alternating drier and wetter periods within the palaeomire during peat accumulation. The fine-scale variability in the δ13C signature appears to be controlled by plant type. Angiosperm/gymnosperm ratios and Vegetation Index are directly correlated with δ13C isotopic values. Plant type, however, seems to be proximally controlled by water level. Angiosperms were more dominant during times of lower water table or less moist conditions, interpreted to correspond to less negative values of δ13C. The correlation of greater concentrations of gypsum with less negative δ13C values also supports drier conditions. However, in addition to the fine-scale variability, four larger scale cycles are defined based on less negative δ13C values. A less negative δ13C isotopic signature demarcates the top of each of these cycles, which represent spikes of lower water table and/or drier conditions. In addition, a general correlation of the δ13C variations in the studied coal seam with atmospheric CO 2 suggests that the atmosphere also had a significant influence on peat formation in the Mile Basin. Although the Mile Basin palaeomire accumulated over a long time, an integrated approach to its analysis has demonstrated considerable variation in palaeoclimate. Changes in wetness/dryness had a direct effect on the ecological composition of the palaeomire. These floral changes would not have only been restricted to the palaeomire but most likely had a regional influence. Thus, detailed analysis of coals can yield useful, insightful and practical knowledge on past regional palaeoenvironmental conditions, which can then be placed within a global context. [ABSTRACT FROM AUTHOR]