The ultra-high mass resolving power and high mass accuracy of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) have been shown to be well suited for the characterization of highly complex mixtures. Petroleum mixtures, arguably the most complex on the planet, have been extensively characterized by FT-ICR MS. This new field of "Petroleomics", spearheaded by the Ion Cyclotron Resonance group at the National High Magnetic Field Laboratory, presents the opportunity to address both fundamental aspects of petroleum chemistry as well as costly upstream and downstream processing issues.
Field desorption ionization (FD) provides access to non-polar hydrocarbons and low-polarity sulfur constituents of petroleum not accessible by the more common electrospray ionization (ESI). Chapter 2 describes the complete automation of the NHMFL 9.4 Tesla FD FT-ICR mass spectrometer and the benefits thereof. Automation allows ensemble averaging for increased dynamic range, mass accuracy, S/N and unattended sample analysis.

The decrease in light "sweet" crude oils has led to the use of heavier, more heteroatom rich feedstocks for the production of petroleum products. The oil sands bitumen deposits in Alberta, Canada represent a substantial reserve of recoverable crude oil. However, the high viscosity and high heteroatom content present production issues of this heavy oil. In particular, the high acid content (termed naphthenic acids) of Athabasca bitumen results in reduced market price due to the possibility of acid induced refinery corrosion (naphthenic acid corrosion). In Chapter 3 the characterization of organic acids in Athabasca bitumen and its heavy vacuum gas oil (HVGO) by negative-ion ESI FT-ICR MS are described. Advantages of acid isolation by ion-exchange chromatography are also discussed.