Photocatalytic pre-treatment with food-grade TiO₂ increases the bioavailability and bioremediation potential of weathered oil from the Deepwater Horizon oil spill in the Gulf of Mexico

Using the 2010 Deepwater Horizon oil spill in the Gulf of Mexico as an impetus, we explored the potential for TiO₂-mediated photocatalytic reactive oxygen species (ROS) generation to increase the bioavailability (solubility) and biodegradability of weathered oil after a spill. Food grade TiO₂, which is FDA approved for use as food additive in the United States, was tested as a photocatalyst for this novel application. Photocatalytic pre-treatment (0.05wt.% TiO₂, UV irradiation 18Wm^-2, 350-400nm) for 24h in a bench top photoreactor increased the soluble organic carbon content of weathered oil by 60%, and enhanced its subsequent biodegradation (measured as O₂ consumption in a respirometer) by 37%. Photocatalytic pre-treatment was also tested outdoors under sunlight illumination, but no significant increase in solubility or biodegradation was observed after 11d of exposure. Although sunlight irradiation of food-grade TiO₂ generated ROS (assessed by the degradation of 4-chlorophenol as a probe compound), the efficacy of weathered oil pre-treatment was apparently hindered by sinking of the photocatalysts under quiescent conditions and illumination occlusion by the oil. Overall, results indicate that photocatalytic pre-treatment to stimulate bioremediation of weathered oil deserves further consideration, but controlling the buoyancy and surface hydrophobicity of the photocatalysts will be important for future efforts to enable ROS generation in proximity to the target compounds.