Determination of oxygen, nitrogen, and sulfur-containing polycyclic aromatic hydrocarbons (PAHs) in urban stream sediments

Recent studies indicate that PAH transformation products such as ketone or quinone-substituted PAHs (OPAHs) are potent aryl hydrocarbon receptor (AhR) activators that elicit toxicological effects independent of those observed for PAHs. Here, we measured eight OPAHs, two sulfur-containing (SPAH), one oxygen-containing (DBF), and one nitrogen-containing (CARB) heterocyclic PAHs (i.e. ΣONS-PAHs = OPAH8 + SPAH + DBF + CARB) in 35 stream sediments collected from a small (∼1303 km²) urban watershed located in south-central Pennsylvania, USA. Combined ΣONS-PAH concentrations ranged from 59 to 1897 μg kg⁻¹ (mean = 568 μg kg⁻¹; median = 425 μg kg⁻¹) and were 2.4 times higher in urban versus rural areas, suggesting that activities taking place on urban land serve as a source of ΣONS-PAHs to sediments. To evaluate urban land use metrics that might explain these data, Spearman rank correlation analyses was used to evaluate the degree of association between ΣONS-PAH concentrations and urban land-use/land-cover metrics along an urban-rural transect at two spatial scales (500-m and 1000-m upstream). Combined ΣONS-PAH concentrations showed highly significant (p < 0.0001) correlations with ΣPAH19, residential and commercial/industrial land use (RESCI), and combined state and local road miles (MILES), suggesting that ΣONS-PAHs originate from similar sources as PAHs. To evaluate OPAH sources, a subset of ΣONS-PAHs for which reference assemblages exist, an average OPAH fractional assemblage for urban sediments was derived using agglomerative hierarchal cluster (AHC) analysis, and compared to published OPAH source profiles. Urban sediments from the Condoguinet Creek (n = 21) showed highly significant correlations with urban particulate matter (X² = 0.05, r = 0.91, p = 0.0047), suggesting that urban particulate matter is an important OPAH source to sediments in this watershed. Results suggest the inclusion of ΣONS-PAH measurements adds value to traditional PAH analyses, and may help elucidate and refine pollutant source identification in urban watersheds.