Environmental and Petrochemical Applications of Ultra-High Resolution FT-ICR Mass Spectrometry

Over the past 20 years, advances in modern ultra-high resolution mass spectrometry have forever changed the expectations of petroleum analyses. Facilitated by advances in ionization methods (that enable molecular-level analysis irrespective of initial or final boiling point), ultra-high resolution Fourier Transform Ion Cyclotron Resonance mass spectrometry (FT-ICR MS) routinely resolves and identifies tens-of-thousands of species (at the level of elemental composition assignment) in individual petroleum samples, by accurate mass measurement alone. As a result, high field FT-ICR MS has been used to revisit, and ultimately support a decades old theory of the composition of petroleum (the Boduszynski Continuum) and expose the compositional constraints (in class, type, and carbon number) imposed by boiling point. Such compositional information facilitates the accurate boiling point prediction of individual elemental compositions based on mass measurement alone, and is now poised to push forward to the molecular-level modeling of heavy ends (Petroleomics). The structural continuum is completed through the infrared multi-photon dissociation of mass isolated segments, and reveals both island (single aromatic core) and archipelago (multi-aromatic core) molecules. Thus, the current results strongly suggest that the decades-old Boduszynski model, which was largely ignored, is in fact correct, and the Yen-Mullins structural model, which is now largely accepted, is in fact, incorrect. The methods and techniques highlighted in the petroleum applications above are shown to have similar, impactful applications in environmental science, specifically in the detailed compositional analysis / understanding of weathering processes encountered after oil spills. This research was made possible in part by a grant from The Gulf of Mexico Research Initiative, by NSF Division of Materials Research through DMR-11-57490, State of Florida, Florida State University, and the Future Fuels Institute.