Source apportionment of polychlorinated biphenyls in the sediments of the Delaware River.

Polychlorinated biphenyls (PCBs) are toxic, persistent, bioaccumulative compounds that threaten water quality in many areas, including the Delaware River. In 2003, total maximum daily loads for PCBs were promulgated for the tidal portion of the river, requiring the collection of a massive and unprecedented data set on PCBs in an urban estuary using state of the art, high-resolution high mass spectrometry (EPA method 1668 revision A). In previous publications, this data set has been examined using positive matrix factorization (PMF) to apportion PCB sources in the air, water, and permitted discharges to the river. Here, the same technique is used to apportion PCB sources in the sediment. This holistic approach allows the comparison of source types and magnitudes to the air, water, and sediment, and allows conclusions to be drawn about the cycling of PCBs in a typical urbanized estuary. A data set containing 87 chromatographic peaks representing 132 PCB congeners in 81 samples and 6 duplicated samples was analyzed. Seven factors were resolved. Three represent relatively unweathered Aroclors. Two were related to the non-Aroclor sources of diarylide yellow pigments and titanium tetrachloride production. The two remaining factors were probably originally related to Aroclors, but they are so highly weathered as to be unrecognizable as Aroclors, and thus have probably resided in the river for a long time. Comparing the abundance of the resolved PCB factors in the air, water, discharges, and sediment demonstrates that high molecular weight formulations, such as Aroclor 1260 and PCBs 206, 208, and 209 produced during titanium tetrachloride synthesis accumulate preferentially in the sediment, in keeping with their greater hydrophobicity. In contrast, lower molecular weight formulations, including the products of PCB dechlorination occurring in sewers, do not accumulate appreciably. PCB 11 from pigment use does accumulate in sediments and also seems to be distributed throughout the estuary via the atmosphere.