Organic sulphur in macromolecular sedimentary organic matter. II. Analysis of distributions of sulphur-containing pyrolysis products using multivariate techniques

This study describes the analysis of sulphur-containing products from Curie-point pyrolysis (Py) of eighty-five samples (kerogens, bitumen, and petroleum asphaltenes and coals) using gas chromatography (GC) in combination with sulphur-selective detection. Peak areas of approximately forty individual organic sulphur pyrolysis products (OSPP) were measured, and the results analysed with the aid of multivariate data reduction techniques (principal components analysis, (PCA)). The structural relationships proposed in an earlier publication ( Sinninghe Damste et al., 1989a) in which OSPP can be grouped according to common “carbon skeletons” are supported by PCA. The distribution of OSPP varies both as a function of kerogen type (as defined by elemental composition) and maturity, reflecting differences in the relative abundance of the various carbon skeleton types. Sulphur-containing products from Type I, Type II, and, to some extent, Type II-S kerogens are dominated by OSPP derived from “moieties” (i.e., discrete structural components within the macromolecule) possessing linear carbon skeletons, while coals and Type III kerogens give rise to higher relative abundances of OSPP with branched carbon skeletons. Type I kerogens are distinguished from Type II kerogens due to the type of linear carbon skeleton, the former yielding higher relative amounts of 2-n-alkylthiophenes and thiolanes and the latter 2,5-di-substituted sulphur-containing products. Products from sulphur-rich (Type II-S) kerogens differ by higher relative abundances of OSPP derived from precursors with isoprenoid and/or steroidal side-chain carbon skeletons, and by higher absolute abundances of all OSPP. Petroleum and, to a lesser extent, bitumen asphaltenes give rise to OSPP with longer carbon skeletons than do kerogens or coals. This observation supports the models proposed by Sinninghe Damste et al. (1990a) in which sulphur-containing moieties in asphaltenes are bound by fewer intermolecular bridges (i.e., are less extensively cross-linked) and, consequently, more readily yield longer chain products on pyrolysis. From these observations, we suggest that Py-GC in combination with PCA provides useful information concerning the chemical nature of organically bound sulphur in geomacromolecules. This information can be rationalised based on carbon skeleton relationships established for low molecular weight organic sulphur compounds, and in terms of kerogen type and overall sulphur content