Elevated nitrate promoted photodegradation of PAHs in aqueous phase: Implications for the increased nutrient...

Polycyclic aromatic hydrocarbons (PAHs) are frequently released in aqueous phase by oil spill or from other sources, and photochemical oxidation is one of their major weathering processes. In this study, the photochemical behavior of phenanthrene (PHE, as a representative PAH) were studied and the effects of nitrogenous compounds were evaluated. The results showed that nitrate was an effective photosensitizer for improving the photodegradation of PHE, but the promoting effect was less effective in seawater due to the presence of halogen ions; the ammonia played a negligible role on PHE degradation. The photochemical ionization was a key process for PHE degradation, it can be retarded due to the quenching of triplet excited state by dissolved oxygen, and the inhibition was most prominent in fresh water. The presence of nitrate increased the steady state concentration of •OH from 2.08 × 10^-15 M to 1.04 × 10^-14 M in fresh water, and from 1.5 × 10^-16 M to 2.08 × 10^-15 M in seawater. The secondary-order reaction rate constant between PHE and •OH (k_•OH,PHE) was determined as 5.70 × 10⁹ M^-1 s^-1. Similar trend was observed for ¹O₂. The contribution of •OH to PHE removal was more prominent in fresh water than in seawater due to the quenching effects of halogen, and the increasing of nitrate enlarged the contribution of •OH. Two possible PHE degradation pathways were proposed based on GC-MS analysis and DFT calculation. The Quantitative Structure-activity Relationship (QSAR) evaluation showed that some degradation intermediates were more toxic than PHE, but the total environmental risk was still diminished due to the low percentage of toxic intermediates. This study provided theoretical and experimental insights into the influence of nitrogenous compounds on the photodegradation of PHAs in water environment.