Abstract--A wide range of novel diagenetic and catagenetic products of the diaromatic carotenoid isorenieratene, a pigment of the photosynthetic green sulphur bacteria Chlorobiaceae, has been identified in a number of sedimentary rocks ranging from Ordovician to Miocene. Compound identification is based on NMR, mass spectrometry, the presence of atropisomers, and stable carbon isotopes. Atropisomers contain an axially chiral centre which, in combination with other chiral centres, results in two or more diastereomers that can be separated on a normal GC column. Chlorobiaceae use the reverse TCA cycle to fix carbon, so that their biomass is enriched in 13C. High ~3C contents of isorenieratene derivatives therefore support their inferred origins.Isorenieratene derivatives include C4o, C33, and C32, diaryl isoprenoids and short-chain aryl isoprenoids with additional aromatic and/or S-containing rings. C33 and C32 compounds are diagenetic products of C33 and C32 "carotenoids" formed from isorenieratene during early diagenesis through expulsion of toluene and m-xylene, respectively. Cyclisation of the polyene acyclic isoprenoid chain can proceed via an intramolecular Diels-Alder reaction, followed by aromatisation of the newly formed ring. Sulphurisation is also an important process during early diagenesis, competing with expulsion and cyclisation. Sulphur-bound isorenieratane is released during progressive diagenesis, due to cleavage of relatively weak S-S and C-S bonds. Cleavage of C-C bonds during aromatisation of newly formed rings and during catagenesis yields short-chain compounds. The inherent presence of a conjugated double bond system in carotenoids implies that similar diagenetic and catagenetic reactions can occur with all carotenoids.Chlorobiaceae live at or below the oxic/anoxic boundary layer and require both light and H2S. The presence of isorenieratene or its diagenetic and catagenetic products in ancient sedimentary rocks and crude oils is therefore an excellent indication for photic zone anoxia in the depositional environment. Diagenetic and catagenetic products of isorenieratene are expected to find applications in reconstruction of palaeoenvironments and in oil-oil and oil-source rock correlation studies. Their presence in several petroleum source rocks suggests that anoxia is an important environmental parameter for the preservation of organic matter.

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Selected sodium salts of functionalized fatty acids were subjected to Curie-point pyrolysis and their pyrolysis products subsequently analyzed by gas chromatography/mass spectrometry in order to study the thermal dissociation mechanisms of lipid moieties in bio-and geomacromolecules.Pyrolysis of the sodium salts of hydroxy and keto acids yields in each case a methylketone as the major product, which is generated via a concerted, six-membered ring rearrangement triggered by the functionality in the alkyl chain. The thermal dissociation of alkylbenzene and alkylthiophene moieties proceeds mainly via hydrogen abstraction at the Xand ;I-carbon atoms, followed by /I-scission.The ratios of the main product pairs, i.e. styrene/toluene and vinylthiophene/2-methylthiophene, are largely controlled by radical mobility during pyrolysis. The major fragmentation pathway of monounsaturated alkyl chains is /I-cleavage adjacent to the double bond. The identification of both Z and E isomers of alkenes in the pyrolysates demonstrates that the initial stereospecifity of the double bond is not retained during pyrolysis. The formation of linear alkylbenzenes from non-phenylic precursor moieties (e.g. diunsaturated fatty acids) shows that specific alkylbenzenes in Curie-point pyrolysates are not always derived from monoaromatic precursors. The addition of organic or mineral matter suppresses these secondary processes. The extension of the model compound results to the recognition of specific types of pyrolysis products and their relevance to the reconstruction of structures of lipid moieties in natural biomacromolecules in kerogens and coals are discussed.