Aspects of Sporinite Chemistry

With the recent advent of the ability to separate coal into maceral concentrates of high purity, the individual constituents of coal can now be analyzed separately, without their mutual interference, giving a much better understanding of the macromolecular structure of coal. The sporinites from two Pennsylvanian age coal samples (Illinois Basin, U.S.A.) were studied, one from a vitrinite-rich high-volatile bituminous coal, the other from a liptinite-rich high-volatile bituminous coal of slightly higher rank. Sporinites were isolated from each coal by density gradient centrifugation. The sporinite of the vitrinite-rich coal was compared chemically and petrographically with the parent coal and with the sporinite of the liptinite-rich coal. The fluorescence spectrum of the sporinite from the liptinite-rich coal is shifted to the red end of the spectrum, which may be accounted for by the somewhat higher rank of the sample and/or by differences in the original assemblage of spores. The lack of chemical differences between the extracts of the sporinite and its whole coal reinforce the concept of bitumen as an homogeneous mobile phase pervading the coal. Thus, extract chemistry seems an unsuitable technique for distinguishing between macerals from the same coal. Hopane and sterane distributions in the sporinite and parent coal pyrolyzates are very similar, but the two materials can be readily distinguished by the distribution of tetracyclic diterpanes of the phyllocladane type, which are biological marker compounds derived from higher plant material. Overall, the sporinite is considerably more paraffinic in character and has a greater preponderance of straight-chain alkane moieties than the coal as a whole. In the case of the vitrinite-rich coal, the whole-coal structure appears significantly more polyaromatic than the sporinite. The distributions of thiophenic compounds differ in the pyrolyzates of the two materials. The sporinite from the liptinite-rich coal is even less polycondensed than the sporinite from the vitrinite-rich sample. The chemical and petrographic differences of the two sporinites probably reflect the different assemblages of spores in the original peats and their different diagenetic histories

Characterization of Organic Sulfur Compounds in Coals and Coal Macerals

Peroxyacetic acid oxidation has been used to investigate the type and distribution of organic sulfur species in samples of vitrinite, sporinite and inertinite, separated from the Herrin No.6 and an Indiana No.5 coal seam. It was established that organic sulfur species were selectively preserved during oxidation and their analysis led to some of the first sulfur-33 NMR spectra obtained for coal. The effects of maceral separation processes on model compounds were also studied. Results from our studies support the following conclusions: 1). Different macerals have different distributions and types of organic sulfur species. 2). Organic sulfur compounds in coal occur at the ends of macromolecular structures. 3). Maceral separation techniques do not affect organic sulfur species in coal. 4). Maceral separation is essential for the chemical characterization of coal. 5). GC-MS and sulfur-33 NMR data agree

Speciation of Heteroatoms in Coal by Sulfur- and Nitrogen-Selective Techniques

The peroxyacetic acid oxidation products from a series of coals of organic sulfur content 0.5-9.8 wt% were examined. The distributions of organic S and N compounds were determined by gas chromatography with sulfur-selective flame photometric and nitrogen-selective thermionic specific detection respectively. A selected sample was also examined in greater detail using low-voltage high-resolution mass spectrometry. The distribution of organic sulfur compounds in the oxidation products was remarkably similar for all the coals. The number of sulfur compounds detected was small compared with that of organic nitrogen compounds detected. This suggests that the sulfur chemistry of coal is considerably simpler than its nitrogen chemistry. Analysis of the m.s. data, together with a comparison of sulfur-selective and nitrogen-selective chromatograms, indicated that a significant proportion of the heteroatomic species present in coal contain more than one heteroatom. This is significant, because few models of coal structure incorporate such species

Speciation of Heteroatoms in Coal by Sulfur- and Nitrogen-selective Techniquestrogen-selective Techniques

The peroxyacetic acid oxidation products from a series of coals of organic sulfur content 0.5-9.8 wt% were examined. The distributions of organic S and N compounds were determined by gas chromatography with sulfur-selective flame photometric and nitrogen-selective thermionic specific detection respectively. A selected sample was also examined in greater detail using low-voltage high-resolution mass spectrometry. The distribution of organic sulfur compounds in the oxidation products was remarkably similar for all the coals. The number of sulfur compounds detected was small compared with that of organic nitrogen compounds detected. This suggests that the sulfur chemistry of coal is considerably simpler than its nitrogen chemistry. Analysis of the m.s. data, together with a comparison of sulfur-selective and nitrogen-selective chromatograms, indicated that a significant proportion of the heteroatomic species present in coal contain more than one heteroatom. This is significant, because few models of coal structure incorporate such species