| High-resolution electrospray ionization Fourier Transform Ion Cyclotron Mass Spectrometry (ESI FT-ICR MS) is a robust method for identifying polar nitrogen, sulfur, and oxygen (-NSO) containing compounds in naturally occurring complex mixtures as it affords an average mass resolution m/Deltam 50% ≥100, 000 and mass accuracy <0.3 ppm. For years, the petroleum industry has suffered financial losses because of surface- and interface-active polar organics. In Chapter 3, we apply ESI FT-ICR MS to track compositional changes in crude oil polar -NSO compounds induced by in-reservoir microbial degradation. We reveal evidence of extensive degradation of -NSO species, previously regarded as resistant to degradation. Chapter 4, characterizes -NSO species mass, heteroatom class, type (rings plus double bonds), and carbon number distribution in the light, middle, and heavy distillates from an acidic vacuum gas oil to mark compositional trends with increased distillation temperature.; Many -NSO species threaten environmental wellness if exposed to aquatic ecosystems. In Chapters 5 and 6, we explore the solubility limitations of crude oil organic acids and bases in fresh and seawater, regarding heteroatomic class, aromaticity, and molecular weight through negative- and positive-ion ESI and Field Desorption FT-ICR MS. Of the 7,000+ singly-charged acidic species identified in South American crude oil, surprisingly many are water-soluble, and much more so in pure water (1,441) than in seawater (768). Many of water-soluble crude oil classes are surface active and stabilize water-in-oil emulsions as shown in Chapter 7 by complimentary use of negative- and positive-ion ESI FT-ICR MS. We investigate the changes in non-volatile acidic and basic water-in-bitumen emulsion stabilizers, with respect to bitumen concentration in heptol diluent. Highly condensed aromatic basic and acidic species stabilize high bitumen concentration emulsions. Emulsion species are less aromatic in low bitumen concentration emulsion films. In Chapter 8, we identify non-volatile polar acidic and basic emulsion stabilizers in nine geographically distinct light, medium, and heavy oils. Independent of parent oil abundances, Ox and OxSy species preferentially adsorb to the oil/water interface. Negative-ion nitrogen containing classes have low interfacial activity. However all positive-ion nitrogen containing species indiscriminately adsorb to the oil/water interface. |
