Petroleum films exposed to sunlight produce hydroxyl radical.

Sunlight exposed oil films on seawater or pure water produced substantial amounts of hydroxyl radical as a result of irradiation. Oil was collected from the surface of the Gulf of Mexico following the Deepwater Horizon spill and exposed to simulated sunlight in thin films over water. Photochemical production of hydroxyl radical was measured with benzoic acid as a selective chemical probe in the aqueous layer. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. The total amount of hydroxyl radical produced in 24 h irradiations of thin oil films over Gulf of Mexico water and pure water were 3.7×10(-7) and 4.2×10(-7) moles respectively. Steady state concentrations of hydroxyl radical were measured using a competition kinetics approach. Hydroxyl radical concentrations of 1.2×10(-16) to 2.4×10(-16) M were observed for seawater and pure water under oil films. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. The addition of TiO2 nanoparticles dramatically changed the observed formation rate of hydroxyl radical in the systems with NP water at pH 3, showing increased formation rate in many cases. With photocatalyst, the steady state concentration of radical decreased, predominantly due to an increase in the hydroxyl radical scavenging rate with oxide present. This study illustrates that oil is a strong and important source of hydroxyl radical when exposed to sunlight. The fate of oil and other dissolved species following oil spills will be heavily dependent on the formation and fate of hydroxyl radical.

Photolytic and photocatalytic degradation of surface oil from the Deepwater Horizon spill.

The photochemical behavior of Deepwater Horizon oil collected from the surface of the Gulf of Mexico was studied. Thin oil films on water were subjected to simulated sunlight, and the resulting chemical and optical changes were observed. Polycyclic aromatic hydrocarbons (PAHs) showed substantial photodegradation, with larger PAHs being more rapidly decomposed. About 60% of the fluorescence at the excitation and emission maxima was observed with 12h of simulated solar irradiation equivalent to approximately 3d of sunlight. Synchronous scan fluorescence measurements showed 80-90% loss of larger PAHs with 12h of simulated solar irradiation. Absorbance of the oil decreased by only 20% over the same time period. Alkanes showed no significant photochemical losses. After irradiation, the toxicity of water in contact with the oil significantly increased, presumably due to the release of water soluble photoproducts that were toxic. Photocatalyst addition resulted in enhanced degradation rate for PAHs, and toxicity of the aqueous layer was altered in the presence of photocatalysts added to the oil film. Photochemistry is an important pathway for degradation of large PAHs, which are typically resistant to biodegradation.