Natural Asphalt Seeps Are Potential Sources for Recalcitrant Oceanic Dissolved Organic Sulfur and Dissolved Black Carbon

Natural oil seepages contribute about one-half of the annual petroleum input to marine systems. Yet, environmental implications and the persistence of water-soluble hydrocarbons from these seeps are vastly unknown. We investigated the release of oil-derived dissolved organic matter (DOM) from natural deep sea asphalt seeps using laboratory incubation experiments. Fresh asphalt samples collected at the Chapopote asphalt volcano in the Southern Gulf of Mexico were incubated aerobically in artificial seawater over 4 weeks. The compositional changes in the watersoluble fraction of asphalt-derived DOM were determined with ultrahighresolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) and by excitation-emission matrix spectroscopy to characterize fluorescent DOM (FDOM) applying parallel factor (PARAFAC) analysis. Highly reduced aliphatic asphalt-derived DOM was readily biodegraded, while aromatic and sulfur-enriched DOM appeared to be less bioavailable and accumulated in the aqueous phase. A quantitative molecular tracer approach revealed the abundance of highly condensed aromatic molecules of thermogenic origin. Our results indicate that natural asphalt and potentially other petroleum seepages can be sources of recalcitrant dissolved organic sulfur and dissolved black carbon to the ocean.

Automated summary

Natural oil seepages contribute a significant amount of petroleum input to marine systems, and the environmental implications and persistence of water-soluble hydrocarbons from these seeps are not well understood. This study investigated the release of oil-derived dissolved organic matter (DOM) from natural deep sea asphalt seeps, finding that aliphatic asphalt-derived DOM was readily biodegraded, while aromatic and sulfur-enriched DOM appeared to be less bioavailable and accumulated in the aqueous phase.