175 Time dependence of aldehyde and ketone oxocarboxylic acid photoproduct generation from crude oil-seawater systems under solar irradiation

Elsheref M., Cao X., Tarr M.A. (2024) Journal of Hazardous Materials, 472, art. no. 134427,  DOI: 10.1016/j.jhazmat.2024.134427

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.

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