Twenty years later: PBDEs in fish from U.S. sites with historically extreme contamination.

Shortly after their production ban PBDE environmental levels retreated from their peak (circa 2000), but rates of decrease appear to be slowing. Therefore, to update environmental PBDE trends, this study re-examined a U.S. riverine system found in 1999 to have the highest PBDE fish tissue (fillet) burdens in the world. Archived 2018-2020 fish tissues were analyzed for PBDEs and results compared to 1999-2000 and 2007 levels. On a positive note, levels decreased by >75% over 20 years. However, PBDEs were still detectable at each collection site (n = 16) and in 93% of the samples. The highest PBDE level (16,300 ng g-1 lipid weight) was observed in fish from the Dan R., downstream from the Hyco R. (where the world's highest level was previously reported). Levels within Hyco R. fish have declined at an annual rate of 30% through 2007. However, reductions during the subsequent 12 years have diminished to only 1.2%. Fillet levels since 2007 actually increased at an estimated annual rate of 8% immediately downstream from the Hyco R. Congener profiles varied between species, likely due to hepatic enzyme debromination, indicating single congener-based health risk evaluations may not be sufficiently protective. Within North America, PBDE fish levels in this freshwater system were twice those of North America's Great Lakes and exceeded by 10-fold those in carp examined from Illinois, USA., another historical hotspot. Average fish PBDE levels also exceed maxima observed in European and Asian riverine systems and were 1000's of times higher than the environmental quality standard (EQS) set by European Parliament (0.0085 ng g-1 wet weight, aquatic biota). Therefore, to protect human health and the environment, PBDE monitoring should remain a priority for regulatory agencies with the goal to identify and eliminate their source and to consider their potential health impacts in the context of other co-existing (emerging and legacy) contaminants.

Assessment of legacy and emerging contaminants in an introduced catfish and implications for the fishery.

Since introduction into the Chesapeake Bay watershed in the 1970s, blue catfish (Ictalurus furcatus) populations have increased, impacting native species. One strategy suggested to limit their growing numbers is to expand the existing commercial fishery. However, the promotion of human consumption of this large, omnivorous fish may increase exposure to contaminants of concern (COC). However, there are few published data on contaminants in blue catfish. To evaluate this possibility, we measured COC (PCBs, PBDEs, OCs, Hg) in individual fillets and compared levels to established consumption advisory limits. James River (near Richmond, Virginia) and Upper Potomac River (downstream of Washington DC) fish exhibited higher burdens of most COC than those from the lower James and rural Rappahannock rivers. Fish sex and δ15N values (surrogate for trophic position) did not correlate with COC concentrations. Potomac River fish exhibited greatest δ15N, perhaps related to local wastewater inputs. Despite differences in human population densities among watersheds, fish mercury (Hg) levels were similar. Most fillets surpassed US EPA advisory limits for unrestricted consumption (> 16 meals/month) for Hg and PCBs. Hg and PCB advisories in the region typically restrict consumption to two 220 g meals/month. Hence, individuals who rely on fish for a large portion of their diet may be exposed to unacceptable Hg and PCB concentrations. COC levels typically increased with fish length; in particular, fish > 550 mm often exceeded unrestricted consumption limits for chlordanes and DDTs. PBDEs, pentachloroanisole, hexachlorobenzene, and mirex levels were generally below established advisories. However, because fish advisories are based on the expected consequences from single contaminants and a single or limited number of toxicological endpoints, consumers face greater risks due to cumulative effects from all coincident COCs, as well as additional exposure pathways, such as other food and air. The additional data on contaminant levels reported here will increase the accuracy of forecasted risks. However, it also illustrates the complexity in communicating the risks from multi-contaminant exposure.

Polybrominated diphenyl ethers in U.S. sewage sludges and biosolids: temporal and geographical trends and uptake by corn following land application.

Polybrominated diphenyl ethers (PBDEs) have been used extensively to flame-retard polymers and textiles. These persistent chemicals enter wastewater streams following manufacture, use, and disposal, concentrating in the settled solids during treatment. Land application of stabilized sewage sludge (known as biosolids) can contribute PBDEs to terrestrial systems. Monitoring sludge/biosolids contaminant burdens may be valuable in revealing trends in societal chemical usage and environmental release. In archived Chicago area sludges/biosolids from 1975 to 2008, penta-BDE concentrations increased and then plateaued after about 2000. Penta-BDE manufacture in the United States ended in December 2004. Deca-BDE concentrations in biosolids rose from 1995 to 2008, doubling on a 5-year interval. Evaluation of U.S. Environmental Protection Agency Targeted National Sewage Sludge Survey data from 2006 to 2007 revealed highest penta-BDE biosolids levels from western and lowest from northeastern wastewater treatment plants (2120 and 1530 µg/kg, respectively), consistent with patterns reported in some recent indoor dust and human blood studies. No significant regional trends were observed for deca-BDE concentrations. Congener patterns in contemporary Chicago biosolids support the contention that BDE-209 can be dehalogenated to less brominated congeners. Biosolids application on agricultural fields increased PBDE soil concentrations. However, corn grown thereon did not exhibit measurable PBDE uptake; perhaps due to low bioavailability of the biosolids-associated flame retardants.

Do temporal and geographical patterns of HBCD and PBDE flame retardants in U.S. fish reflect evolving industrial usage?

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) are common flame retardants in polymers and textiles. Recognition of the persistent, bioaccumulative, and toxic properties of PBDEs has prompted reductions in their use. In contrast, HBCD has received less scrutiny. The U.S has historically been a dominant BFR consumer. However, the few publications on HBCD in wildlife here suggest modest levels compared to Asian and European studies. In contrast, the HBCD concentrations we detected in U.S. fish are among the highest reported in the world. The temporal trends observed suggest that HBCD use may have risen, and that of Penta-BDE declined, following the 2004 termination of its U.S. manufacture. For example, Hyco River carp collected in 1999-2002 exhibited a mean ∑HBCD (sum of α-, ß- and γ-HBCD) concentration of only 13 ng/g (lipid weight basis), but was 4640 ng/g in fish collected in 2006-2007. In contrast, the mean ∑PBDE level in these same fish decreased from 40,700 ng/g in 1999-2002 to 9140 ng/g in 2006-2007. Concentrations of HBCD and PBDEs in several Hyco River fish species exceeded those from rivers less influenced by manufacturing outfalls. Results support the contention that textile-related production, relative to its BFR market share, may release disproportionately large amounts of HBCD to the environment.

Kepone in James River fish: 1976-2002.

In late 1975, it was discovered that a manufacturing facility had not only exposed workers to the chlorinated pesticide, Kepone, but had also severely contaminated the James River estuary. To assess the potential for the public to be exposed to Kepone through the consumption of contaminated seafood, the Commonwealth of Virginia initiated a finfish-monitoring program in late 1975. Over 13,000 samples have been collected and analyzed as part of this effort. Kepone levels in most species began falling when the production of Kepone ended, but the average concentrations remained over the action limit of 0.3 microg g(-1) wet weight until the early 1980s. By 1988 few fish contained Kepone concentrations greater than the action limit. Kepone is still detected in the majority of white perch and striped bass samples taken from the James River and a fish consumption advisory is still in effect thirty years after the source of contamination was removed.

Semipermeable membrane devices accumulate conserved ratios of sterane and hopane petroleum biomarkers.

Semipermeable membrane devices (SPMDs) are commonly used as a time-integrated measure of aqueous concentrations of persistent hydrophobic chemicals, including PAH, pesticides, dioxins, and PCBs. Another class of persistent hydrophobic chemicals is petroleum biomarker compounds (hopanes and steranes) that are used for hydrocarbon source identification and allocation. In this study three different passive sampling device designs were exposed to a complex hydrocarbon mixture (Alaska North Slope crude) in a laboratory experiment to determine uptake rates of biomarkers into SPMDs. In addition to the standard triolein filled SPMDs, iso-octane filled SPMDs (ISPMDs) and unfilled low-density polyethylene strips (PESDs) were tested. Uptake rates and effective sampling rates were determined for 53 compounds. There was little variation in sampling rates among the individual biomarkers; average values (ld(-1)) for hopanes were 0.43+/-0.07 (PESD), 0.33+/-0.06 (SPMD), and 0.44+/-0.03 (ISPMD) and average sterane sampling rates were 0.57+/-0.04 (PESD), 0.42+/-0.03 (SPMD), and 0.53+/-0.03 (ISPMD). The primary reason for biomarker analysis is for source discrimination of petroleum. Nineteen different diagnostic ratios were measured, and were found to be remarkably well conserved between the oil, water, and all three devices. This indicates that SPMDs, PESDs, and ISPMDs should each be effective for source discrimination studies of petroleum contamination.

Calibration and field verification of semipermeable membrane devices for measuring polycyclic aromatic hydrocarbons in water.

The use of semipermeable membrane devices (SPMDs) has become common in environmental sampling of nonpolar organic contaminants, yet few data exist for the uptake or sampling rates of polycyclic aromatic hydrocarbons (PAH). Two separate laboratory calibration experiments were conducted to determine the sampling rates of 28 individual PAH and 19 homologues. PAH with a log Kow > 4.5 remained in the linear uptake phase for 30 days, but PAH with a log Kow < 4.5 began to approach steady state within 15 days. Sampling rates, corrected for dissolved organic carbon, ranged from 2.11 to 6.06 L d(-1). Shear flow across the membrane had no statistically significant effect on rates over the range of 0.01-0.50 cm s(-1). Field verification of these sampling rates yielded agreement within about a factor of 2 for most PAH and a factor of 4 for all PAH. The worst agreement was for the most hydrophobic PAH, where partitioning into dissolved and particulate organic carbon pools are more important and less certain. These SPMD sampling rate data will allow quantitative estimations of freely dissolved concentrations of 47 compounds that are commonly used for PAH and petroleum product source identification and allocation.