Alterations in fingerprints of polychlorinated biphenyls in benthic biota at the Portland Harbor Superfund Site (Oregon, USA) suggest metabolism

doi:10.1016/j.chemosphere.2019.02.039

Chemosphere

Volume 223, May 2019, Pages 74-82

https://doi.org/10.1016/j.chemosphere.2019.02.039 Get rights and content

Highlights

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Congener patterns of PCBs in benthic biota from the Portland Harbor Superfund Site were analyzed.
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Paired samples of sediment and biota showed differences in PCB fingerprints and congener ratios.
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These differences imply metabolism via the cytochrome P450 pathway in clams, worms, and mussels.

Abstract

In order to understand the sources and fate of polychlorinated biphenyls (PCBs) in several species of benthic biota, including clams (Corbicula fluminea), oligochaetes (Lumbriculus variegatus), and mussels (Margaritifera falcata and Anodonta nuttalliana) at the Portland Harbor Superfund Site (PHSS), their congener fingerprints were examined. First, diagnostic ratios of congeners known to be metabolizable vs. recalcitrant in the cytochrome P450 (CYP) pathway were significantly lower in biota than in its co-located sediment, indicating metabolism may have occurred. Next, the congener patterns were analyzed using Positive Matrix Factorization (PMF). The dominant fingerprint (by mass) in benthic biota is related to Aroclor 1260 but displays differences in the fingerprint that are consistent with weathering via absorption, distribution, metabolism, and excretion (ADME). This fingerprint is similar to one isolated from PCBs in fish from Washington State, indicative of common metabolic pathways and consistent with CYP metabolism. When metabolism is taken into account, the spatial distribution of the PMF-isolated PCB fingerprints in biota matches well with those from co-located sediment samples, suggesting that the same mix of sources at one location partitions into biota and sediment. In accordance to their higher hydrophobicity, higher molecular weight (MW) PCB formulations were proportionately more abundant in biota than in sediment, although low MW PCBs (e.g., PCBs 4 and 11) do bioaccumulate in benthic organisms and should not be ignored in risk assessment efforts. Finally, fingerprinting suggests potential reasons why lab-based and field-based biota-sediment accumulation factors (BSAFs) differ substantially for bivalves.

Introduction

The Portland Harbor Superfund Site (PHSS) is one of many contaminated sites in the United States, where polychlorinated biphenyls (PCBs) are a main contaminant of concern (USEPA, 2016). There are over 60 facilities on the harbor that may be sources of contamination (USEPA, 2016). These are shown in figure S-1 of supporting information. Given the large number of potentially responsible parties, a better understanding of the sources of PCB contamination at this site is essential. To further this objective, Rodenburg et al. (2015c) conducted fingerprinting analysis of the 209 PCB congeners, measured in the water column and sediment of the PHSS, using EPA Method 1668 (USEPA, 2003). The present work extends this fingerprinting analysis to include benthic biota in order to determine whether PCB sources remain recognizable in biota, and to what extent these sources impact biota, relative to sediment and water.

By fingerprinting PCB profiles in multiple environmental compartments, the relative importance of sources to different media can be assessed. This has been attempted, for example, in the Delaware River basin and the New York/New Jersey Harbor, where PCB signatures have been investigated in air (Praipipat et al., 2017), water (Du et al., 2008; Rodenburg et al., 2011), sediment (Praipipat et al., 2013; Rodenburg and Ralston, 2017), and permitted discharges (Rodenburg et al., 2010a, 2012). In these systems, however, there was insufficient data to perform fingerprinting analysis on the biota. One location where fingerprinting of PCBs in biota has been performed is the Hanford Site in Washington State (Rodenburg et al., 2015a). Unfortunately, the data on PCBs in the water and sediment at the Hanford site are not sufficient for fingerprinting analysis. Thus, the PHSS presents a unique opportunity to link PCB signatures in benthic biota with those in co-located sediment and water samples. It is particularly important to compare biota and sediment fingerprints, because absorption, distribution, metabolism, and excretion (ADME) processes can alter PCB fingerprints in biota.

The overall objective of this study was to understand how PCB profiles in the water column and sediment, investigated in our previous work (Rodenburg et al., 2015c), affect local benthic biota. Source apportionment, using Positive Matrix Factorization (PMF), was conducted on PCBs in biota in order to compare the dominant PCB sources in biota with those observed in the water column and sediment. In addition, specific ratios of PCB congeners in biota, diagnostic to metabolic activity, support PMF analysis and provide mechanistic insight into PCB biotransformation processes in aquatic invertebrates.

Section snippets

Materials and methods

Portland Harbor is a tidal estuary that is home to the City of Portland, Oregon, with a population of about 600,000 (see map, Supporting Information Figure S-1). The current study area extends from River Mile (RM) 1.9 to 11.8, where RM 0 is defined as the confluence of the Willamette and Columbia rivers. (Figure S-1). Data were obtained from the PHSS Remedial Investigation (RI) database (provided as Appendix F of USEPA, 2016).

Results

Total PCB (ΣPCB) concentrations in the 130 samples of benthic biota ranged from 2100 pg/g to 3,800,000 pg/g ww (non-detects set to zero).

Conclusions

PCB congener fingerprints in the biota generally remain similar to the unweathered Aroclors (Fig. 1), allowing the apportionment of these sources with a satisfactory degree of confidence. Aroclor 1260 appears to undergo the greatest degree of alteration via ADME processes, but the fingerprint resulting from these processes still resembles Aroclor 1260 well enough to be recognizable. In addition, this ADME-altered Aroclor 1260 fingerprint is similar to the one found at the Hanford Site (Fig. 1),

Acknowledgements

This was an unfunded study. The authors thank Jennifer L. Peterson at the Oregon Department of Environmental Quality (ODEQ) for help in understanding the PCB dataset and Lawrence P. Burkhard at the EPA Mid-Continent Ecology Division (MED) Laboratory for providing the EPA's BSAF Dataset Version 1.00. We also thank Kevin Farley for helpful insights.

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Alterations in fingerprints of polychlorinated biphenyls in benthic biota at the Portland Harbor Superfund Site (Oregon, USA) suggest metabolism

Highlights

Abstract

Introduction

Section snippets

Materials and methods

Results

Conclusions

Acknowledgements

Mar. Environ. Res.

Mar. Environ. Res.

Chemosphere

Mar. Environ. Res.

Mar. Environ. Res.

Aquat. Toxicol.

Anal. Chim. Acta

Environ. Pollut.

Chemosphere

Chemosphere

Chemosphere

Regul. Toxicol. Pharmacol.

Factors influencing the rate of polychlorinated biphenyl dechlorination in Hudson River sediments

Environ. Sci. Technol.

Concentration levels and congener profiles of polychlorinated biphenyls, pentachlorobenzene, and hexachlorobenzene in commercial pigments

Environ. Sci. Pollut. Control Ser.

A food web bioaccumulation model for organic chemicals in aquatic ecosystems

Environ. Toxicol. Chem.

Polychlorinated biphenyls in aquatic sediments: environmental fate and outlook for biological treatment

A case study for microbial biodegradation: anaerobic bacterial reductive dechlorination of polychlorinated biphenyls—from sediment to defined medium

Annu. Rev. Microbiol.

Concentration-dependent changes of PCB patterns in fish-eating mammals: structural evidence for induction of cytochrome P450

Arch. Environ. Contam. Toxicol.

Comparing laboratory- and field-measured biota-sediment accumulation factors

Integrated Environ. Assess. Manag.

Evaluation of PCB bioaccumulation by Lumbriculus variegatus in field-collected sediments

Environ. Toxicol. Chem.

PCB loading from sediment in the hudson river: congener signature analysis of pathways

Environ. Sci. Technol.

Patterns of bioaccumulation of polybrominated diphenyl ether and polychlorinated biphenyl congeners in marine mussels

Environ. Sci. Technol.

Source apportionment of polychlorinated biphenyls in the tidal Delaware River

Environ. Sci. Technol.

Questions of size and numbers in environmental research on microplastics: methodological and conceptual aspects

Environ. Chem.

Biotransformations of aroclor 1242 in hudson river test tube microcosms

Appl. Environ. Microbiol.