Direct and indirect photolysis of polycyclic aromatic hydrocarbons in nitrate-rich surface waters

The photolysis of three polycyclic aromatic hydrocarbons (PAHs)-pyrene, phenanthrene, and naphthalene-were studied in waters taken from creosote-contaminated sites in Gary (IN, USA) and Wilmington (NC, USA). Direct photolysis of all PAHs was observed under simulated solar radiation, with pyrene degrading at a faster rate than either phenanthrene or naphthalene. Phenanthrene degradation, when compared to its direct photolysis rate, increased in Gary water but decreased in Wilmington water. Analysis of the waters for dissolved organic carbon (DOC) and nitrate revealed higher levels of DOC in the Wilmington sample (9.29 mg/L) compared with the Gary sample (6.73 mg/L), as well as significantly less nitrate (0.046 mM vs 0.205 mM for the Gary sample). The slightly lower rate of phenanthrene degradation observed for the Wilmington sample, corrected for light attenuation effects, is statistically the same as that in the direct photolysis experiments. Therefore, we attribute the lower rate of degradation in the presence of Wilmington water to light screening by DOC, but we believe the faster reaction rate observed for the Gary water results from hydroxyl radical (OH*) chemistry generated by nitrate photolysis. Indeed, degradation of the target compound increased when nitrate (at 0.2 and 0.4 mM) was added to the Wilmington sample, further corroborating this conclusion. Overall photoreaction rates decreased for the lower-molecular-weight PAHs, because the fastest naphthalene photolytic rate was roughly two orders of magnitude slower than that of pyrene.