• GC × GC–TOFMS analysis used to characterize aryl isoprenoids and diagenetic carotenoids. • Application of high temperature GC × GC for structured resolution of biomarkers. • Isorenieratane, chlorobactane and diagenetic derivatives found in Cretaceous crude oils. • Photic zone euxinia (PZE) occurred in rifted South Atlantic marginal basins. • Molecular geochemical indicators of green sulfur bacteria revealed by GC × GC–TOFMS. Diagenetic aromatic carotenoids and degradation products, which are derived from the carotenoids of photosynthetic sulfur bacteria, were characterized in the aromatic fraction of Brazilian Cretaceous crude oils (NE Brazil, Sergipe-Alagoas Basin) by high-temperature comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (HT-GC × GC–TOFMS). Unresolved complex mixtures (UCM), coeluting compounds, and limited mass spectrometric identification were noted by traditional one-dimensional (1D) GC–MS screening of aromatic compounds. Group-type separation on a two-dimensional chromatographic plane, first- and second-dimension retention times (1t R and 2t R , respectively), and mass spectra enabled the assignment of alkylated mono-, di-, tri-, and tetra-aryl hydrocarbons with confidence. A series of diagenetic C 40 carotenoids and degraded products, which are likely indicators for green-brown sulfur bacteria, were detected. This finding corroborates previous results, and isorenieratane was relatively more abundant than 2,3,6-trimethylaryl isoprenoids. Moreover, atropisomeric biphenyls (m / z 237), which coeluted using 1D GC–MS analyses, were resolved by GC × GC and identified by mass spectrometry. The identification of minor abundances of chlorobactane, diagenetic biphenyl chlorobactane, and related compounds, for the first time in these Brazilian Cretaceous oils, may indicate a contribution of green sulfur bacteria (Chlorobiaceae) and photic zone euxinia in shallow waters. [ABSTRACT FROM AUTHOR]