Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum.

Asphaltenes are high-boiling and recalcitrant compounds that are generally minor components of crude oil (∼0.1-15.0 wt %) but dominate the composition of heavily weathered spilled petroleum. These solid residues exhibit a high structural complexity, comprised of polycyclic aromatic hydrocarbons (PAHs) that are a mixture of single-core (island) and multicore (archipelago) structural motifs. The mass fraction of each motif is sample-dependent. Thus, knowledge of a potential structural dependence (single- versus multicore) on the production of water-soluble species from asphaltene samples is key to understanding the contribution of photochemically generated dissolved organic matter from oil spills. In this work, asphaltene samples with enriched mass fractions of either island (single-core) or archipelago (multicore) structural motifs are photo-oxidized on artificial seawater by the use of a solar simulator. Molecular characterization of oil- and water-soluble photoproducts, conducted by Fourier transform ion cyclotron resonance mass spectrometry, reveals that island motifs exhibit very limited production of water-soluble species, and their oil-soluble products reflect the molecular composition of the starting material. Conversely, archipelago motifs yield a water-soluble compositional continuum of Ox, SxOy, and NxOy containing hydrocarbons species that exhibit the typical molecular fingerprint of dissolved organic matter (DOM). The lower carbon number and aromaticity of the archipelago-derived asphaltene photoproducts suggest the occurrence of photofragmentation (or photolysis) reactions. To investigate the possibility of the opposite reaction (photopolymerization), the photo-oxidation of small PAHs isolated from a low-boiling petroleum distillation cut was also performed. It yielded water-soluble compounds with carbon number and aromaticity up to 2-fold higher than the starting material, strongly suggesting that polymerization (addition reactions) occurs. Collectively, the results indicate that the presence of archipelago motifs and the occurrence of cracking/polymerization reactions are central in the production of dissolved organic matter from fossil fuels.