Geochemical significance of alkylbenzene distributions in flash pyrolysates of kerogens, coals and asphaltenes

Abstract

The distribution of C0-C5 alkylbenzenes in flash pyrolysates of forty-seven immature kerogens and coals from different geographical locations and of different ages were studied using gas chromatography (GC) in combination with mass spectrometry (MS) in order to decipher the origin of aromatic moieties in macromolecular matter. All possible structural isomers of the alkylated benzenes were determined, and, in some cases, absolute yields were calculated. Sulphur-rich (Type II-S) kerogens yield higher absolute amounts of alkylbenzenes in comparison to Type I, II, and III kerogens. The variations in internal distribution patterns of C2-C4 alkylbenzenes were analyzed using multivariate analysis techniques (principal component analysis; PCA). Major variations in alkylbenzene distributions were due to an increased abundance of specific alkylbenzenes, which are related to specific precursor moieties in the macromolecular structure assuming that they are mainly formed via -cleavage. Alkylbenzenes possessing 'linear' carbon skeletons are enhanced in flash pyrolysates of Guttenberg and Estonian Kukersite kerogens (Type I) and are proposed to be derived from linear precursors which have undergone cyclization/aromatization. Relatively high amounts of 1,2,3,4- and 1,2,3,5-tetramethylbenzenes were found in flash pyrolysates of Womble and Duvernay kerogens (Type II) which are likely to be derived from macromolecularly bound diaromatic carotenoids. The relatively high abundance of 1,2,3-trimethylbenzene and 1,3-/1,4-dimethylbenzene in pyrolysates of Monterey kerogens (Type II-S) is proposed to be indicative of the presence of bound nonaromatic carotenoids (e.g., ,-carotene) which have undergone aromatization and/or loss of methyl groups upon diagenesis. 1-methyl-4-isopropylbenzene, which appears in relatively high amounts in flash pyrolysates of Walcott Chuar kerogen (Type II) and Catalan coals (Type III), is thought to be derived from a heteroatom-bound precursor. These results demonstrate that the structure of monoaromatic moieties in kerogen is biologically controlled. The internal distribution patterns of alkylbenzenes of flash pyrolysates of kerogens and asphaltenes show a marked resemblance, the latter showing a slight enhancement of alkylbenzenes with longer carbon skeletons. These observations support the idea that asphaltenes are structurally related to kerogen and that aromatic moieties in asphaltenes are bound by fewer intermolecular bridges.