ABSTRACT
Aldehyde and ketone oxocarboxylic acid photoproducts were semi-quantitated in the aqueous phase after subjecting Macondo (MC252) crude oil-seawater systems to simulated solar irradiation. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was applied after derivatizing the samples with 2,4-dinitrophenylhydrazine (DNPH). Oil-seawater was irradiated at 27.0 °C using a solar simulator for 1 to 18 h. Following irradiation, the aqueous phase was treated with DNPH to generate aldehyde-DNPH and ketone-DNPH derivatives. Solid-phase extraction enriched the samples before analyzing them using (-) ESI-MS/MS. Precursor and product ion spectra were used to select carboxylic acid-containing aldehydes and ketones and provide semi-quantitation using surrogate standards and an internal standard. Loss of m/z 44 (CO2) in the product ion spectra further confirmed the carboxylic acid character. Near-linear increases in photoproduct concentration in the aqueous phase were observed over the 18 h irradiation period. Among the aldehyde and ketone oxocarboxylic acid photoproducts studied, photoproduction rates ranged from 0.6 - 69 µmol/h·m2 of oil surface. Despite some fluctuations, a general trend of lower production rate with higher molecular weight was observed. These results demonstrate the near-linear dependence of photoproduction on irradiance and provide ranges of rates that can be applied to modeling aldehyde and ketone oxocarboxylic acid photoproduction in ocean spills. STATEMENT OF ENVIRONMENTAL IMPACT: Crude oil on seawater degrades when exposed to sunlight. Oxygenated molecules are produced, including carboxylic acid-containing aldehydes and ketones. The formation of these photoproducts from oil films behaves linearly with solar exposure time. These photoproducts are more soluble than the original oil molecules, allowing them to have increased bioavailability and potentially increased toxicity. The rate of formation of these species when oil is exposed to sunlight determines their environmental impact.
ABSTRACT
Oil spills represent a major source of negative environmental impacts in marine systems. Despite many decades of research on oil spill behavior, photochemistry was neglected as a major factor in the fate of oil spilled in marine systems. Subsequent to the Deepwater Horizon oil spill, numerous studies using varied approaches have demonstrated the importance of photochemistry, including short-term impacts (hours to days) that were previously unrecognized. These studies have demonstrated the importance of photochemistry in the overall oil transformation after a spill and more specifically the impacts on emulsification, oxygenation, and microbial interactions. In addition to new perspectives, advances in analytical approaches have allowed an improved understanding of oil photochemistry after maritime spill. Although the literature on the Deepwater Horizon spill is extensive, this review focuses only on studies relevant to the advances in oil photochemistry understanding since the Deepwater Horizon spill.
