New insight into environmental photochemistry of PAHs induced by dissolved organic matters: A model of naphthalene in seawater

Abstract

The photochemical behavior of a model PAH, naphthalene, was investigated under simulated sunlight irradiation with different dissolved organic matter (DOM) in seawater. The results revealed that naphthalene was prone to direct photolysis (Φd = 1.34 × 10-3) and could be degraded by 3DOM*/1O2-induced reactions with fulvic acid (FA) and humic acid (HA) at low concentrations. However, the DOM at a high level dramatically decreased the kobs due to the higher light attenuation and radical competition effect. The presence of FA resulted in lower 3DOM*/1O2 generation and quantum yield compared with HA, but it achieved higher degradation kinetics due to the higher reactivity between 3FA* and naphthalene and their lower binding effect. The naphthalene degradation in natural water with different depths and DOM were modeled based on the experimental results, which revealed the important role of indirect photolysis initiated by inorganic constituents. Moreover, several degradation intermediates were identified by GC-MS and three possible pathways were proposed. The Quantitative Structure Activity Relationships (QSAR) evaluation revealed that some intermediates are more toxic than original naphthalene. This study offers further insights into the photochemical behavior of PAHs, which will facilitate our understanding of the persistence and ecological risks of organic contaminants in natural waters.