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]