Quantitative source apportionment of PAHs in sediments of Little Menomonee River, Wisconsin: weathered creosote versus urban background.

Polycyclic aromatic hydrocarbons (PAHs) in urban environments are often derived from point and nonpoint sources, the latter collectively considered as urban background. Quantifying the contributions of point sources and urban background is important for managing and remediating urban sediments. In this work, the sources of PAHs in 350 sediments from a 1.5-mile portion of the Little Menomonee River (Milwaukee, WI) were determined using principal component analysis (PCA), chemical fingerprinting, and positive matrix factorization (PMF), the combination of which mitigates weaknesses of any one method. At issue was quantifying the contributions of a creosote point-source formerly located 3.5 to 5.0 miles upstream versus urban background-derived PAHs in the sediments. In total, creosote and urban background contributed 27 and 73% (+/-14%) of eight carcinogenic PAHs (CPAHs), respectively, in this part of the River. The concentrations of CPAHs derived from urban background were highest in surface sediments (0-6 in.; 20 +/- 17 mg/kg), particularly near major roadway crossings, increased in the downstream direction, and (on average) exceeded the 15 mg/kg regulatory cleanup threshold. Weathered creosote-derived CPAHs were widespread at low concentrations (4.8 +/- 8.1 mg/kg) although some discrete sediments, mostly at depths below 6 in., contained elevated CPAHs derived from creosote. This work demonstrates the value of combining multiple techniques in source apportionment studies in urban sediments. It further demonstrates a means to determine the concentration of PAHs attributable to nonpoint sourced background in urban sediments without the need to identify, collect, and analyze (assumedly) "representative" background samples, which may not even exist in heterogeneous urban watersheds.