Influence of maceral content on δ13C and δ15N in a Middle Pennsylvanian coal

Using density-gradient centrifugation, within-sample heterogeneity in C/N, δ13C, and δ15N was determined for a sample of the Blue Gem coal bed (Middle Pennsylvanian, Duckmantian (Westphalian B), Breathitt Formation) and related to maceral (petrographically identifiable organic component) composition. Relatively pure macerals were separated by density, with purities up to 99% in the case of vitrinite in fractions around 1.3 g/mL. Lower density fractions (∼ 1.2 g/mL) contain predominantly liptinite (∼ 75%) but also significant amounts of vitrinite (∼ 20%). Denser fractions contain increasing amounts of inertinite, with several fractions between 1.37 and 1.44 g/mL containing > 98% total inertinite. Within these denser fractions, semifusinite concentrated at lower densities than did fusinite. The separation of macerals by density allowed a more detailed evaluation of the isotopic composition of relatively pure macerals within a single coal. δ13C becomes increasingly heavy across the density gradient, with δ13C values being lightest in the liptinites, followed by vitrinite, and then semifusinite and fusinite; by contrast, δ15N becomes lighter across the same density range. C/H increases with density, reflecting a general decrease in aliphatic components and increase in aromatic components. C/N follows a similar pattern, ranging from < 40 to over 100, increasing significantly at densities > 1.32, the point at which inertinite macerals begin to predominate over vitrinite.The isotopic composition of macerals reflects chemical composition, which in turn reflects: 1) the original composition of plant tissues from which the macerals originated; 2) early diagenetic changes; and 3) changes during coalification. Macerals derived from lipid-rich precursor materials (liptinites) have more depleted δ13C values (∼ 2‰) relative to those derived from woody tissues (vitrinite). Fusinized material, derived from fossil charcoal, has δ13C values enriched by ∼ 0.5‰ compared with the vitrinite, consistent with the results from combustion experiments using modern plant tissues. Vitrinite fractions have enriched δ15N values relative to inertinite fractions, which may reflect early diagenetic changes in woody tissues involving preferential loss of 14N, possibly due to bacterial activity during the peat-forming stage. Due to the within-sample variability in carbon isotopic composition reported here, it is suggested that chemostratigraphic studies based on Type III kerogen (including both dispersed organic matter and coals) carefully consider the associated effects of variability in maceral composition.