Characterization of Highly Oxygenated and Environmentally Weathered Crude Oils by Liquid Chromatography Fourier Transform Ion Cyclotron Mass Spectrometry (FT-ICR MS)

Abstract

Heavy and biodegraded oils exhibit an ever increasing oxygen complexity. Electrospray ionization (ESI) coupled to FT-ICR MS highlights the most acidic and basic oxygen species; however, quantitative and qualitative information about less polar oxygenated compounds is essential to understand both the source and, potentially, the modification pathways for oxygenated crude oils. Liquid chromatography (LC) is complementary to FT-ICR MS to deconvolve crude oils according to oxygen functionality, thereby enriching oxygen species that are not easily ionized or are present in low abundance. Ketones and carboxylic acids dominate most environmentally modified crude oils; however, phenols and polyphenols are also important intermediates in both biotic and abiotic modifications. Moreover, due to the nature of the refinement process, oxygen-containing species and their intermediates can serve as chemical tracers in produced water streams and areas of rapid thermal changes that lead to gum or deposit formation. Here, we describe an analytical separation scheme for an environmentally weathered (highly oxygenated) crude oil designed to highlight carboxylic acid isolation and ketone enrichment, as well as the separation of other oxygen compounds by polarity. Experimental A weathered beach extract collected from the coast of Florida was fractionated by LC and analyzed by FT-ICR MS. LC techniques are designed to target specific oxygen functionalities (e.g., ketones, alcohols, phenols, and carboxylic acids). The mass spectra of the LC fractions were acquired with a custom-built 9.4 T FT-ICR Instrument. Positive and negative electrospray ionization serve to highlight basic and acidic oxygen species. Preliminary DataLC fractionation was performed with a silicic acid stationary phase. Four fractions correspond to aromatics, neutral nitrogen, basic nitrogen, and polar compounds. Positive ESI FT-ICR MS indicated a relative abundance for the O1 heteroatom class ranging from 2% in the whole beach extract to 12 % in the neutral nitrogen fraction. The increased relative abundance of O1 compounds suggests the enrichment of ketones from the original sample. Carboxylic acids are isolated by retention on an amine stationary phase and subsequent elution with a mixture of dichloromethane, methanol, and formic acid. Oxygen species will be further probed with new separation schemes to focus on analysis of phenols.