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.

Evidence for widespread dechlorination of polychlorinated biphenyls in groundwater, landfills, and wastewater collection systems.

One of the few pathways for environmental transformation of polychlorinated biphenyls (PCBs) is microbial dechlorination under anaerobic conditions, which is reported to occur in contaminated sediments of rivers, lakes and harbors. The goal of this work was to determine whether PCB dechlorination occurs in built waste treatment environments. We analyzed a large database on PCB congener concentrations in effluents and some influents of facilities in the Delaware River Basin. Positive matrix factorization was used to identify the sources of PCBs and to look for evidence of dechlorination. Seven factors were resolved from the data set of 89 congeners in 645 samples. Two of the resolved factors represented dechlorination signals. One of these was dominated by PCBs 4 and 19 and represents an advanced stage of dechlorination of Aroclors to di- and trichlorinated congeners. This dechlorination signal was most prevalent in effluents from sites with contaminated groundwater and from wastewater treatment plants (WWTPs) that serve combined sewers or treat landfill leachate. The other dechlorination signal appeared to represent an intermediate stage of dechlorination, because it was dominated by two coeluting groups of tetrachlorinated congeners: PCBs 44 + 47 + 65 and 45 + 51. This partial dechlorination signal was most prevalent in the 40 WWTPs with separate (sanitary) sewer systems, where it often comprised more than 20% of the PCBs in the effluents. Both dechlorination signals were present in WWTP influents, but were not observed in stormwater runoff, suggesting that dechlorination occurs in sewers. This work represents the first convincing evidence of PCB dechlorination occurring outside of contaminated aquatic sediments or anaerobic digesters. The results suggest that PCBs are dechlorinated by anaerobic bacteria in sewers, landfills, and contaminated groundwater. These two dechlorination signals comprise about 19% of the total loads of PCBs to the Delaware River from the sampled dischargers.

Evidence for unique and ubiquitous environmental sources of 3,3'-dichlorobiphenyl (PCB 11).

The non-Aroclor congener 3,3'-dichlorobiphenyl (PCB 11) has been recently detected in air, water, biota, sediment, and suspended sediment. Although it has been known since at least the 1970s that this congener is produced inadvertently during the production of diarylide yellow pigments, this work presents the first evidence that the use of these pigments in consumer goods results in the dispersion of PCB 11 throughout the environment at levels that are problematic in terms of achieving water quality standards for the sum of polychlorinated biphenyls (PCBs). In this work, PCB 11 is measured at ppb levels in consumer goods that are likely to be discarded in ways that allow them to enter wastewater treatment plants and combined sewer overflows, including newspapers, magazines, cardboard boxes used for food packaging, and plastic bags. Also, using data sets acquired for the purpose of calculating total maximum daily loads (TMDLs) for PCBs, PCB 11 loads to the New York/New Jersey Harbor and Delaware River are calculated. Despite the fact that there are no known manufacturers of diarylide yellow pigments in the Delaware River watershed, the loads of PCB 11 to the Delaware River exceed the TMDL for the sum of PCBs by nearly a factor of 2. The ratio of PCB 11 to a characteristic dechlorination end product, PCB 4 (2,2'-dichlorobiphenyl), in these data sets indicates that dechlorination is not a significant source of PCB 11 in these systems. In the upper Hudson River, where extensive dechlorination of heavy PCB congeners occurs, the ratio is just 0.012. In contrast, downstream in the NY/NJ Harbor as well as in the Delaware River the ratio is much higher and more variable. Pigment use therefore appears to be the main source of PCB 11 in these systems, and this congener is likely to present a significant obstacle to achieving PCB water quality standards throughout the United States.

Direct and indirect atmospheric deposition of PCBs to the Delaware River watershed.

Atmospheric deposition can be an important source of PCBs to aquatic ecosystems. To develop the total maximum daily load (TMDL) for polychlorinated biphenyls (PCBs) for the tidal Delaware River (water-quality Zones 2-5), estimates of the loading of PCBs to the river from atmospheric deposition were generated from seven air-monitoring sites along the river. This paper presents the atmospheric PCB data from these sites, estimates direct atmospheric deposition fluxes, and assesses the importance of atmospheric deposition relative to other sources of PCBs to the river. Also, the relationship between indirect atmospheric deposition and PCB loads from minor tributaries to the Delaware River is discussed. Data from these sites revealed high atmospheric PCB concentrations in the Philadelphia/Camden urban area and lower regional background concentrations in the more remote areas. Wet, dry particle, and gaseous absorption deposition are estimated to contribute about 0.6, 1.8, and 6.5 kg year-(-1) sigmaPCBs to the River, respectively, exceeding the TMDL of 0.139 kg year(-1) by more than an order of magnitude. Penta-PCB watershed fluxes were obtained by dividing the tributary loads by the watershed area. The lowest of these watershed fluxes are less than approximately 1 ng m(-2) day(-1) for penta-PCB and probably indicates pristine watersheds in which PCB loads are dominated by atmospheric deposition. In these watersheds, the pass-through efficiency of PCBs is estimated to be on the order of 1%.