Greenhouse gases generated from the anaerobic biodegradation of natural offshore asphalt seepages in southern California

Significant offshore asphaltic deposits with active seepage occur in the Santa Barbara Channel offshore southern California. The composition and isotopic signatures of gases sampled from the oil and gas seeps reveal that the coexisting oil in the shallow subsurface is anaerobically biodegraded, generating CO₂ with secondary CH₄ production. Biomineralization can result in the consumption of as much as 60% by weight of the original oil, with ¹³C enrichment of CO₂. Analyses of gas emitted from asphaltic accumulations or seeps on the seafloor indicate up to 11% CO₂ with ¹³C enrichment reaching +24.8‰. Methane concentrations range from less than 30% up to 98% with isotopic compositions of –34.9 to –66.1‰. Higher molecular weight hydrocarbon gases are present in strongly varying concentrations reflecting both oil-associated gas and biodegradation; propane is preferentially biodegraded, resulting in an enriched ¹³C isotopic composition as enriched as –19.5‰. Assuming the 132 million barrels of asphaltic residues on the seafloor represent ~40% of the original oil volume and mass, the estimated gas generated is 5.0×1010 kg (~76×109 m³) CH₄ and/or 1.4×1011 kg CO₂ over the lifetime of seepage needed to produce the volume of these deposits. Geologic relationships and oil weathering inferences suggest the deposits are of early Holocene age or even younger. Assuming an age of ~1,000 years, annual fluxes are on the order of 5.0×107 kg (~76×106 m³) and/or 1.4×108 kg for CH₄ and CO₂, respectively. The daily volumetric emission rate (2.1×105 m³) is comparable to current CH₄ emission from Coal Oil Point seeps (1.5×105 m³/day), and may be a significant source of both CH₄ and CO₂ to the atmosphere provided that the gas can be transported through the water column.