Characterization of Tertiary Catalan lacustrine oil shales: Discovery of extremely organic sulphur-rich Type I kerogens

Abstract

The kerogens of three Tertiary Catalan lacustrine oil shales were analyzed by light microscopy, flash pyrolysis-gas chromatography-mass spectrometry, and bulk composition methods (elemental analysis, Rock Eval pyrolysis). Two of the three kerogens (Ribesalbes and Campins) are extremely rich in organic sulphur (atomic Sorg/C ratio > 0.04) and hydrogen (atomic ratio HC ratio > 1.5) and are, consequently, classified as Type I-S kerogens. Very characteristic distribution patterns of flash pyrolysis products (e.g., alkan-9- and -10-ones, alkadienes) of the Ribesalbes kerogen revealed that it is predominantly composed of fossilized organic matter of the freshwater alga Botryococcus braunii. These two findings demonstrate that sulphurization of organic matter may also occur in lacustrine sediments provided that sulphate is supplied by external sources. Data on the third kerogen sample (Cerdanya) suggest that the freshwater alga Pediastrum may contain a (partly) aromatic biomacromolecule that is selectively preserved upon diagenesis. These findings testify to the large variability in palaeodepositional conditions in lacustrine environments. A comparison of the biomarker composition of the extract of the Ribesalbes oil shale with the kerogen composition indicate that biomarkers often cannot be used to assess the major sources of organic matter in such settings. A similar conclusion can be drawn from a comparison of literature data concerning the Messel Oil Shale.