Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has exposed the ultracomplexity of fossil fuels, thereby validating the compositional trends that rule petroleum distillation, known as the Boduszynski Continuum. Routine FT-ICR MS analysis of a single crude oil sample can reveal tens-of-thousands of unique molecular formulas; however, currently available ionization methods suffer from limitations for such complex mixtures that are not yet completely understood. Simply put, MS detects ions, and thus, it depends heavily on the ability of ion sources to indiscriminately volatilize and subsequently ionize samples of interest. Despite advances in soft ionization methods, the characterization of complex matrices remains a challenge due to the lack of an ion source, commercial or custom-built, that can vaporize and ionize all compounds without bias, save analyte concentration. However, atmospheric pressure photoionization (APPI) has been shown to provide the most uniform ion production for mixtures of petroleum model compounds and real samples, with little to no fragmentation. In this work, we investigated the molecular composition of PetroPhase 2017 asphaltenes and its extrography fractions, with a focus on the total vanadium content and molecular composition of vanadyl porphyrins as a function of aggregate size distribution, accessed through separate experiments: online gel permeation chromatography (GPC) inductively coupled plasma−MS (ICP−MS) and online GPC APPI FT-ICR MS (at 21 T). The results reveal that the extrography separation provides asphaltene fractions (i.e., acetone, Hep/Tol, and Tol/THF/MeOH) enriched in 51 V-containing compounds with distinctive aggregate size distributions. The acetone fraction features smaller aggregate sizes, as it elutes later in the GPC chromatogram than Hep/Tol and Tol/THF/MeOH fractions, and overall, presents up to ∼14-fold higher ionization efficiency in APPI. Such behavior suggests a correlation between aggregate size and production efficiency of monomeric ions in APPI. Bulk compositional trends accessed by GPC separation and highlighted by ICP−MS detection indicate that despite multiple separation steps (i.e. extrography followed by GPC), APPI FT-ICR MS can only access ∼37% of the total V-containing compounds. Although the more stable/larger aggregates dominate the size distributions of all asphaltene samples studied, it is the weakly aggregated/monomeric species that are preferentially observed by APPI-MS. Tendencies in the molecular composition of vanadyl porphyrins and S/O-containing compounds strongly suggest that London forces might be central in the self-assembly process of asphaltene nanoaggregates to produce more massive clusters. The results demonstrate that the observed compositional trends (albeit limited) can be accessed when coupling advanced chromatographic separations with online high-field FT-ICR MS detection.

This study probes the nanoaggregation behavior of asphaltenes by gel permeation chromatography (GPC). Compounds containing sulfur, vanadium, and nickel were monitored online with elemental detection by inductively coupled plasma mass spectrometry (ICP-MS), and four fractions that vary in nanoaggregation state were analyzed by positive atmospheric pressure photoionization 9.4 T Fourier transform ion cyclotron resonance mass spectrometry ((+)APPI FT-ICR MS). We also highlight some of the challenges associated with the analysis of asphaltene fractions by direct infusion. Nanoaggregate size and monomer ion yield were inversely correlated. The extremely low ionization efficiency for the largest aggregate GPC fractions collected from the asphaltenes limited their characterization to only a few of the most abundant heteroatom classes. However, for all of the characterizable heteroatom classes, aggregation closely correlated with increased relative abundance of larger, more aliphatic compounds. These observations agree with results from the parent whole crude oil, suggesting that the interactions among the more alkylated compounds in asphaltenes may be a major contributor to asphaltene nanoaggregation.