RESUMO
Due to the relatively high concentrations of polycyclic aromatic hydrocarbons (PAHs) in oil samples, oil spills in aquatic ecosystems release significant amounts of PAHs. Although remediation efforts often take place during or immediately after an oil spill incident, a portion of the released PAHs remains in the body of water. A natural phenomenon resulting from the direct exposure of PAHs to sunlight is photodegradation. This article investigates the effect of dioctyl sulfosuccinate (DOSS) on the photodegradation of benzo[a]pyrene (BaP), the most toxic PAH in the priority pollutants list of the US Environmental Protection Agency (EPA). DOSS is a surfactant typically used in the remediation of oil spills. Three lamps with maximum emission wavelengths at 350 nm, 419 nm, and 575 nm were individually and simultaneously used to irradiate aqueous solutions of BaP in the absence and the presence of DOSS. When irradiated with the 419 nm lamp or the 575 lamp, BaP showed no photodegradation. Upon irradiation with the 350 nm lamp and with the simultaneous use of the three lamps, the photodegradation of BaP followed first-order kinetics. Independent of the irradiation wavelength, the presence of DOSS increased the half-life of BaP in the aqueous solution. In the case of the 350 nm lamp, the rate constant of photodegradation in the absence and the presence of DOSS varied from (3.79 ± 0.97) × 10-3 min-1 to (1.10 ± 0.13) × 10-3 min-1, respectively. Under simultaneous irradiation with the lamps, the rate constant of photodegradation varied from (1.12 ± 0.35) × 10-3 min (no DOSS) to (3.30 ± 0.87) × 10-4 (with DOSS). Since the largest rate constants of photodegradation were observed in the absence of DOSS, the longer half-lives of BaP in the presence of surfactant were attributed to the incorporation of PAH molecules into the DOSS micelles.
RESUMO
BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) with molecular mass 302 Da are the most investigated PAHs within the high molecular weight PAHs class. This PAH class contributes to a significant portion of the mutagenic and/or carcinogenic response associated to the PAH fraction present in environmental and combustion-related samples. Several reasons prevent the routine analysis of 302 Da PAHs in environmental samples, including large number of possible isomers, limited number of commercially available reference standards, and low concentration levels. RESULTS: These studies search for a newly synthetized dibenzo-fluoranthene of molecular mass 302 Da, namely dibenzo[b,l]fluoranthene, in a standard reference material (SRM 1597a) from the National Institute of Standards and Technology. The eluting behavior of dibenzo[b,l]fluoranthene is investigated under reversed-phase liquid chromatographic conditions for its determination via absorption and fluorescence detection. Vibrationally resolved spectra and fluorescence lifetimes recorded from octane matrices at 77 K and 4.2 K allow for its qualitative and quantitative analysis at the parts-per-trillion concentration levels. Its unambiguous determination is then reported for the first time in the SRM 1597a. SIGNIFICANCE AND NOVELTY: Of the 89 possible 302 Da PAH isomers, only 23 isomers have been identified in SRMs and/or environmental samples. The determination of dibenzo[b,l]fluoranthene in the SRM 1597a takes a step forward to fulfilling this gap.