Characterization of polycyclic aromatic hydrocarbons and their phenanthroperylene quinone precursors in fossil crinoids using liquid chromatography–atmospheric pressure photoionization mass spectrometry

The distribution and origin of diagenetic products of polycyclic quinone pigments in fossil crinoids was investigated using high-performance liquid chromatography–diode array detection–atmospheric pressure photoionization mass spectrometry (HPLC–DAD–APPI-MS). A number of characteristic higher-molecular-weight polycyclic aromatic hydrocarbons (PAHs) were identified in toluene extracts of diverse crinoid samples, with 1,2,3,4,5,6-hexahydrophenanthro[1,10,9,8-opqra]perylene as the main compound. Moreover, phenanthro[1,10,9,8-opqra]perylene-7,14-dione (PPQ) and further derivatives were detected for the first time in the fossil record, representing intermediates between hydroxylated phenanthroperylene quinone pigments such as fringelite F and phenanthroperylene PAHs. The widespread presence of PPQ, its derivatives and related PAHs in fossil crinoids which contain phenanthroperylene quinone pigments confirms the diagenetic formation of specific PAHs by reductive degradation of quinone pigments.