Simultaneous Detection of Vanadyl, Nickel, Iron, and Gallium Porphyrins in Marine Shales from the Eagle Ford Formation, South Texas

Metalloporphyrins in immature shales of the Late Cretaceous Eagle Ford Formation from South Texas were analyzed by positive-ion electrospray ionization (ESI) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Vanadyl, nickel, iron, and gallium porphyrins were detected in a single mass spectrum. The iron porphyrins were most abundant, followed by vanadyl, nickel, and gallium porphyrins, consistent with the metal contents determined by elemental analysis. The distribution of porphyrins shows that deoxophylloerythroetio (DPEP) porphyrins, dicyclic-deoxophylloerythroetio (di-DPEP) porphyrins, and porphyrins containing oxygen functional groups are the main components. The detection of oxygen-containing porphyrins, such as iron porphyrins with formulas of CnHmN4FeO, CnHmN4FeO2, and CnHmN5FeO2, would offer new clues of petroporphyrins formation mechanism from biological sources, such as chlorophylls and hemes. To our knowledge, this reports for the first time the presence of oxygen-containing iron porphyrins and gallium porphyrins in geological samples other than coals and lignites. The discovery of these petroporphyrins could provide additional insights into the diagenetic pathway of petroporphyrins and novel applications in petroleum geochemistry/exploration and oil refining. The composition of metalloporphyrins may potentially provide clues to decipher the redox conditions during deposition in the Eagle Ford Formation and provide better understanding of the Oceanic Anoxic Event 2 (OAE-2).