Ozonation of triterpenoids: Implications for early diagenesis of biomarkers in oxic environments

This study examines the fate of commonly found organic natural products under exposure to ozone to simulate early oxic diagenesis. The model compounds β-amyrin, lupenone and friedelin have been investigated by ozonation in the presence of water. The transformation products were identified or proposed based on their fragmentation patterns in mass spectra. The double bonds located at the isopropenyl group of lupenone and ring C of β-amyrin are the main reaction sites in the ozonation reaction. The major products identified from the ozonation of β-amyrin are β-amyrone, 12,13-epoxyoleanan-3β-ol, 11-oxo-olean-12-en-3β-ol, 12-oxo-oleanan-3β-ol. In addition, 8,14-seco-12-oxo-olean-14-en-3β-ol, 8,14-seco-12-oxo-olean-13-en-3β-ol and 8,14-seco-oleana-3,12-dione, generated from the bond cleavage between C-8 to C-14 of 12-oxo-oleanan-3β-ol and 12-oxo-oleanan-3-one, respectively, have also been detected. 22,29,30-trisnorlup-18(19)-en-3-one, 22,29,30-trisnorlupan-3-one, 22,29,30-trisnorlupana-3,19-dione, 22,29,30-trisnorlupana-3,12-dione, lupeol, lup-22(29)-en-3-on-29-ol, 22,29-epoxylupan-3-one, lupan-3-on-29-al, lupan-3-on-29-ol and 19,22-epoxylupan-3-one are the major products from the ozonation of lupenone. No transformation product was detected for friedelin, probably due to its stability to ozonation.