Abstract-Anew route for the formation of gammacerane from tetmhymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids.

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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Abstract--In a North Sea oil, the carotenoid derivatives/3-carotane,/3-isorenieratane, and isorenieratane were identified, together with a series of aryl isoprenoids with a 2,3,6-trimethyl substitution pattern for the aromatic ring. The 613C values of/~-carotane and/3-isorenieratane are similar, whereas isorenieratane is ca. 15%o heavier. This suggests that/3-isorenieratane is not derived from/~-isorenieratene biosynthesised by Chlorobiaceae, but from aromatisation of/~-carotene. This was confirmed by laboratory aromatisation of partially hydrogenated/~-carotene, which yielded/~-isorenieratane as the main product. The aryl isoprenoids, which can be formed by C-C bond cleavage of both isorenieratane and/~-isorenieratane, have a mixed isotopic signature in the oil. These results indicate that mere identification of aryl isoprenoids, without determination of their 6 ~3C values, cannot be used to assess the presence of Chlorobiaceae, and, thus, photic zone anoxia in the depositional environment.