Probing Aggregation Tendencies in Asphaltenes by Gel Permeation Chromatography. Part 2: Online Detection by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry

This work is the second installment of a study that probes the aggregation behavior of asphaltenes by gel permeation chromatography (GPC). In part 1, analysis of GPC aggregate fractions collected from the 2017 PetroPhase asphaltene sample by direct infusion revealed an inverse correlation between aggregate size and aromaticity. However, characterization of the largest aggregate fractions by direct infusion was hampered by solvent contaminant peaks and dynamic range limitations due to the extremely low ionization efficiencies of the larger, more aliphatic species that comprise those fractions. Here, we couple the GPC separation with online detection by positive atmospheric pressure photoionization ((+)­APPI) 21 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to overcome those problems and reveal that the most abundant species that comprise the largest aggregate segment are indeed the most aliphatic. The ability to characterize difficult-to-analyze samples, like asphaltenes, is the first major advantage of online coupling. Another benefit is the increased chromatographic resolution afforded by online coupling, which enables a finer examination in the most aggregated region and reveals a local trend opposed to the global trend. The very first species to elute in the largest aggregates were more condensed polyaromatic compounds, and the larger, more aliphatic species elute shortly thereafter in much greater relative abundance.