Assessment of PCB contamination, the potential for in situ microbial dechlorination and natural attenuation in an urban watershed at the East Coast of the United States.

Sediment contamination is a major environmental issue in many urban watersheds and coastal areas due to the potential toxic effects of contaminants on biota and human health. Characterizing and delineating areas of sediment contamination and toxicity are important goals of coastal resource management in terms of ecological and economical perspectives. Core and surficial sediment samples were collected from an industrialized urban watershed at the East Coast of the United Stated and analyzed to evaluate the PCB contamination profile and toxicity resulting from dioxin-like PCBs as well as reductive dechlorination potential of indigenous PCB halorespiring bacteria through dechlorination activity assays. To support the experimental results an anaerobic dechlorination model was applied to identify microbial dechlorination pathways. The total PCB concentration in core samples ranged from 3.9 to 225.6 ng/g·dry weight (dw) decreasing with depth compared to 353.2 to 1213.7 ng/g·dw in surficial samples. The results of this study indicated an increase in PCB contamination over the last century as the industrial activity intensified. The toxicity resulting from dioxin-like PCBs was reduced up to 94% in core samples via 21 pathways resulting from the dechlorination model. Dechlorination rates in surficial sediment were between 1.8 and 13.2 ·â€¯10-3 mol% PCB116/day, while lower rates occurred in the core sediment samples. Dechlorination was achieved mainly through meta followed by para dechlorination. However, the rarer ortho dechlorination was also observed. Detection of indigenous PCB dechlorinating bacteria in the sediments and reduction of toxicity indicated potential for natural attenuation when point and nonpoint source PCBs in the urban watershed are controlled and PCB loading reduced.

Development of suspect and non-target screening methods for detection of organic contaminants in highway runoff and fish tissue with high-resolution time-of-flight mass spectrometry.

Untreated urban stormwater runoff contributes to poor water quality in receiving waters. The ability to identify toxicants and other bioactive molecules responsible for observed adverse effects in a complex mixture of contaminants is critical to effective protection of ecosystem and human health, yet this is a challenging analytical task. The objective of this study was to develop analytical methods using liquid chromatography coupled to high-resolution quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) to detect organic contaminants in highway runoff and in runoff-exposed fish (adult coho salmon, Oncorhynchus kisutch). Processing of paired water and tissue samples facilitated contaminant prioritization and aided investigation of chemical bioavailability and uptake processes. Simple, minimal processing effort solid phase extraction (SPE) and elution procedures were optimized for water samples, and selective pressurized liquid extraction (SPLE) procedures were optimized for fish tissues. Extraction methods were compared by detection of non-target features and target compounds (e.g., quantity and peak area), while minimizing matrix interferences. Suspect screening techniques utilized in-house and commercial databases to prioritize high-risk detections for subsequent MS/MS characterization and identification efforts. Presumptive annotations were also screened with an in-house linear regression (log Kowvs. retention time) to exclude isobaric compounds. Examples of confirmed identifications (via reference standard comparison) in highway runoff include ethoprophos, prometon, DEET, caffeine, cotinine, 4(or 5)-methyl-1H-methylbenzotriazole, and acetanilide. Acetanilide was also detected in runoff-exposed fish gill and liver samples. Further characterization of highway runoff and fish tissues (14 and 19 compounds, respectively with tentative identification by MS/MS data) suggests that many novel or poorly characterized organic contaminants exist in urban stormwater runoff and exposed biota.

Evaluating Contaminants of Emerging Concern as tracers of wastewater from septic systems.

Bacterial and nutrient contamination from anthropogenic sources impacts fresh and marine waters, reducing water quality and restricting recreational and commercial activities. In many cases the source of this contamination is ambiguous, and a tracer or set of tracers linking contamination to source would be valuable. In this work, the effectiveness of utilizing a suite of Contaminants of Emerging Concern (CECs) as tracers of bacteria from human septic system effluent is investigated. Field sampling was performed at more than 20 locations over approximately 18 months and analyzed for a suite of CECs and fecal coliform bacteria. The sampling locations included seeps and small freshwater discharges to the shoreline. Sites were selected and grouped according to level of impact by septic systems as determined by previous field sampling programs. A subset of selected locations had been positively identified as being impacted by effluent from failing septic systems through dye testing. The CECs were selected based on their predominant use, their frequency of use, and putative fate and transport properties. In addition, two rounds of focused sampling were performed at selected sites to characterize short-term variations in CEC and fecal coliform concentrations, and to evaluate environmental persistence following source correction activities. The results indicate that a suite of common use compounds are suitable as generalized tracers of bacterial contamination from septic systems and that fate and transport properties are important in tracer selection. Highly recalcitrant or highly labile compounds likely follow different loss profiles in the subsurface compared to fecal bacteria and are not suitable tracers. The use of more than one tracer compound is recommended due to source variability of septic systems and to account for variations in the subsurface condition. In addition, concentrations of some CECs were measured in receiving waters at levels which suggested the potential for environmental harm, indicating that the possible risk presented from these sources warrants further investigation.

Toxicological effects of polychlorinated biphenyls (PCBs) on freshwater turtles in the United States.

Prediction of vertebrate health effects originating from persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) has remained a challenge for decades thus making the identification of bioindicators difficult. POPs are predominantly present in soil and sediment, where they adhere to particles due to their hydrophobic characteristics. Animals inhabiting soil and sediment can be exposed to PCBs via dermal exposure while others may obtain PCBs through contaminated trophic interaction. Freshwater turtles can serve as bioindicators due to their strong site fidelity, longevity and varied diet. Previous research observed the health effects of PCBs on turtles such as decreased bone mass, changed sexual development and decreased immune responses through studying both contaminated sites along with laboratory experimentation. Higher deformity rates in juveniles, increased mortality and slower growth have also been observed. Toxicological effects of PCBs vary between species of freshwater turtles and depend on the concertation and configuration of PCB congeners. Evaluation of ecotoxicological effects of PCBs in non-endangered turtles could provide important knowledge about the health effects of endangered turtle species thus inform the design of remediation strategies. In this review, the PCB presence in freshwater turtle habitats and the ecotoxicological effects were investigated with the aim of utilizing the health status to identify areas of focus for freshwater turtle conservation.

Perfluorinated compounds in the surface waters of Puget Sound, Washington and Clayoquot and Barkley Sounds, British Columbia.

Perfluorinated compounds (PFCs) are persistent organic contaminants detected in various environmental matrices including sediment, air, biota, and water. The objectives of this study was to evaluate the occurrence of these contaminants within the surface waters of the Pacific Northwest region and through relative concentrations and ratios, to assess their possible sources. Surface waters were extracted and analyzed by liquid chromatography tandem mass spectrometry (LCMSMS). Perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were the most commonly detected PFCs. Total PFC concentrations detected ranged from 1.5 to 41 ng L-1. Surprisingly, levels of PFCs in the more urbanized Puget Sound waters were comparable to those measured from the more rural region of Clayoquot and Barkley Sounds in British Columbia. The ratio of PFHpA/PFOA were also similar between the two regions, suggesting that the burden of PFCs throughout the region results from direct input from regional sources.

Diffusive exchange of PAHs across the air-water interface of the Kaohsiung Harbor lagoon, Taiwan.

Instantaneous air-water polycyclic aromatic hydrocarbons (PAHs) exchange fluxes were calculated in 22 pairs of ambient air and water samples from Kaohsiung Harbor lagoon, from December 2003 to January 2005. The highest net volatilization (3135 ng m(-2) day(-1)) and absorptive (-1150 ng m(-2) day(-1)) fluxes in the present study were obtained for the three-ring PAH phenanthrene on 7 April and 27 January 2004, respectively. All PAH diffusive fluxes for three-ring PAHs except phenanthrene were mainly volatilization exchange across the air-water interface. Phenanthrene and the four-ring PAHs were absorbed primarily from the atmosphere and deposited to the surface water, although some minor volatilization fluxes were also observed. Differences in flux magnitude and direction between the dry and wet seasons were also evident for PAHs. Strong absorptive/weaker volatilization PAH fluxes occurred in the dry season, but the opposite was found in the wet season. The mean daily PAH diffusive fluxes were an in flux of -635 ng m(-2) day(-1) in the dry season and an efflux of 686 ng m(-2) day(-1) in the wet season. The integrated absorbed and emitted fluxes of PAHs for harbor lagoon surface waters in the dry and wet seasons were 3.1 kg and 3.4 kg, respectively. Different from water bodies located in temperate zone, phenanthrene diffusive fluxes in Kaohsiung Harbor lagoon was favored in volatilization from surface waters during the wet season (April to September) because of scavenging by precipitation and dilution by prevailing southwesterly winds. In addition, this study used both of salinity and temperature to improve estimation of Henry's law constants (H) of PAHs in a tropical coastal area and show that correction for salinity produced 13-15% of differences in H values.

Kinetics of polychlorinated biphenyl partitioning to marine Chrysophyte Isochrysis galbana.

This study focused on the uptake kinetics of polychlorinated biphenyl (PCB) congeners by the Chrysophyte, Isochrysis galbana. A gas-purging experimental system was used to maintain constant dissolved PCB concentrations. Three phases of absorption were observed: first, a rapid absorption phase within the first 15min, second, a first order process reaching the maximum concentration within 48h of exposure, and third, a plateau phase as yet to be determined with very slight increases in concentration. In this study, the percentage of the maximum concentration reached within the first phase varied from 10% to 67%, depending on the size of the PCB (as determined by molecular weight and total surface area), whereas the uptake rate (k(u)) during the second phase was more comparable across different PCBs. In addition, for the first phase, the bioconcentration factor (BCF) of PCBs deviated from its expected relationship with hydrophobicity, as determined by K(ow), and was instead related to the molecular structure of the compound.

Bioaccumulation kinetics of polybrominated diphenyl ethers from estuarine sediments to the marine polychaete, Nereis virens.

Polybrominated diphenyl ethers (PBDEs) are flame-retardant chemicals that have become ubiquitous environmental contaminants. Polybrominated diphenyl ether no-uptake rates from estuarine or marine sediments to deposit-feeding organisms have not yet been reported. In the present study, the marine polychaete worm Nereis virens was exposed to field-contaminated and spiked sediments containing the penta- and deca-BDE commercial mixtures in a 28-d experiment to characterize the relative bioavailability of PBDE congeners from estuarine sediments. A time series sampling regimen was conducted to estimate uptake rate constants. In both field-collected and laboratory-spiked sediment exposures, worms selectively accumulated congeners in the penta-BDE mixture over BDE 209 and other components of the deca-BDE mixture, supporting the prevalence of these congeners in higher trophic level species. Brominated diphenyl ether 209 was not bioavailable to N. virens from field sediment and was only minimally detected in worms exposed to spiked sediments in which bioavailability was maximized. Chemical hydrophobicity was not a good predictor of bioavailability for congeners in the penta-BDE mixture. Direct comparison of bioavailability from the spiked and field sediments for the predominant congeners in the penta-BDE mixture was confounded by the considerable difference in exposure concentration between treatments. Biota-sediment accumulation factors (BSAFs) for N. virens after 28 d of exposure to the field sediment were lower than the BSAFs for Nereis succinea collected from the field site, indicating that 28-d bioaccumulation tests using N. virens may underestimate the in situ concentration of PBDEs in deposit-feeding species. The bioavailability of PBDEs to N. virens indicates that these chemicals can be remobilized from estuarine sediments and transferred to aquatic food webs.

Polybrominated diphenyl ethers and polychlorinated biphenyls in sediments of southwest Taiwan: regional characteristics and potential sources.

Very little information is available on the contamination of coastal sediments of Taiwan by PBDEs and PCBs. In this study, we determined the concentrations of 19 PBDE and 209 PCB congeners in 57 surface sediment samples to identify the possible sources of PBDEs and PCBs. The total PBDE and PCB concentrations ranged from below detection limit to 7.73 ng/g and 0.88-7.13 ng/g, respectively; these values are within the ranges observed for most coastal sediments worldwide. The PBDE congeners were dominated by BDE-209 (50.7-99.7%), with minor contributions from penta- and octa-BDEs. The signatures of PCB congeners suggested that PCB residues in Kaohsiung coast may be the legacy of past use or the result of ongoing inputs from the maintenance, repair and salvage of old ships. Principal component analysis of the congener-specific composition of PBDEs and PCBs revealed distinct regional patterns that are related to the use of commercial products.

Bioavailability of decabromodiphenyl ether to the marine polychaete Nereis virens.

The flame retardant decabromodiphenyl ether (BDE 209) accumulates in humans and terrestrial food webs, but few studies have reported the accumulation of BDE 209 in aquatic biota. To investigate the mechanisms controlling the bioavailability of BDE 209, a 28-d bioaccumulation experiment was conducted in which the marine polychaete worm Nereis virens was exposed to a decabromodiphenyl ether (deca-BDE) commercial mixture (>85% BDE 209) in spiked sediments, in spiked food, or in field sediments. Bioaccumulation from spiked substrate with maximum bioavailability demonstrated that BDE 209 accumulates in this species. Bioavailability depends on the exposure conditions, however, because BDE 209 in field sediments did not accumulate (<0.3 ng/g wet weight; 28-d biota-sediment accumulation factors [BSAFs] <0.001). When exposed to deca-BDE in spiked sediments also containing lower brominated congeners (a penta-BDE mixture), bioaccumulation of BDE 209 was 30 times lower than when exposed to deca-BDE alone. Selective accumulation of the lower brominated congeners supports their prevalence in higher trophic level species. The mechanisms responsible for limited accumulation of BDE 209 may involve characteristics of the sediment matrix and low transfer efficiency in the digestive fluid.

Lack of biological effects of water accommodated fractions of chemically- and physically-dispersed oil on molecular, physiological, and behavioral traits of juvenile snapping turtles following embryonic exposure.

Snapping turtle (Chelydra serpentina) eggs were exposed to two concentrations of chemically- or physically-dispersed water accommodated fractions of weathered Arabian light crude oil (Low=0.5 and High=10 g oil/L water). Solutions were passed through nest substrate to simulate alterations in composition during percolation to egg depth. Hatchlings were raised for 13 months during which numerous endpoints were measured. Prior to percolation, total PAH ("tPAH"; the sum of 52 PAHs measured) in physically-dispersed oil fractions were similar (High, 43; Low 67 mg/L). Following percolation, tPAH was also similar in physically-dispersed fractions (High, 14; Low 24 mg/L). Addition of dispersant increased tPAH prior to percolation in the High treatment (302 mg/L) relative to Low (13 mg/L), but percolation resulted in nearly equal concentrations in both treatments (High, 30; Low, 22 mg/L) due to physical trapping of dispersed oil by the nest substrate. In both chemically- and physically-dispersed fractions, percolation reduced low molecular weight (MW) compounds such that embryos were exposed to primarily mid- to high MW compounds. Total PAH in eggs differed 15-fold between the chemically-dispersed High and physically-dispersed High treatments (560 and 36 microg/kg respectively), the former characterized by higher MW compounds than the latter. While eggs accumulated up to 560 microg/kg tPAH, we observed no effects on hatching success or hatchling/juvenile traits (DNA integrity, survival, growth, metabolism, energy storage, or behavior), our results demonstrate that PAH profiles are altered during percolation, suggesting that experiments with subsurface organisms should be designed to account for compositional changes that occur as the solutions percolate through the substrate.

Seasonality of diffusive exchange of polychlorinated biphenyls and hexachlorobenzene across the air-sea interface of Kaohsiung Harbor, Taiwan.

Gaseous and dissolved concentrations of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) were measured in the ambient air and water of Kaohsiung Harbor lagoon, Taiwan, from December 2003 to January 2005. During the rainy season (April to September), gaseous PCB and HCB concentrations were low due to both scavenging by precipitation and dilution by prevailing southwesterly winds blown from the atmosphere of the South China Sea. In contrast, trace precipitation and prevailing northeasterly winds during the dry season (October to March) resulted in higher gaseous PCB and HCB concentrations. Instantaneous air-water exchange fluxes of PCB homologues and HCB were calculated from 22 pairs of air and water samples from Kaohsiung Harbor lagoon. All net fluxes of PCB homologues and HCB in this study are from water to air (net volatilization). The highest net volatile flux observed was +172 ng m(-)(2) day(-1) (dichlorobiphenyls) in December, 2003 due to the high wind speed and high dissolved concentration. The PCB homologues and HCB fluxes were significantly governed by dissolved concentrations in Kaohsiung Harbor lagoon. For low molecular weight PCBs (LMW PCBs), their fluxes were also significantly correlated with wind speed. The net PCB and HCB fluxes suggest that the annual sums of 69 PCBs and HCB measured in this study were mainly volatile (57.4 x 10(3) and 28.3 x 10(3) ng m(-2) yr(-1), respectively) and estimated yearly, 1.5 kg and 0.76 kg of PCBs and HCB were emitted from the harbor lagoon surface waters to the ambient atmosphere. The average tPCB flux in this study was about one-tenth of tPCB fluxes seen in New York Harbor and in the Delaware River, which are reported to be greatly impacted by PCBs.

Accumulation and maternal transfer of polychlorinated biphenyls in snapping turtles of the upper Hudson River, New York, USA.

We conducted field studies over three years to assess body burdens and maternal transfer of polychlorinated biphenyls (PCBs) as well as indices of sexual dimorphism in snapping turtles (Chelydra serpentina) of the upper Hudson River (NY, USA.) We collected adult turtles in areas known to be contaminated with PCBs and in nearby reference areas for measurement of body size, precloacal length, and penis size. We analyzed PCB concentrations in eggs collected over three years and in whole blood from adults in one year. Total PCB concentrations (mean +/- standard error) in eggs were 2,800 +/- 520 and 59 +/- 5 ng/g wet weight in the contaminated area and the reference area, respectively. Eggs from the contaminated area were significantly enriched in tri-, penta-, and hepta-PCBs relative to the reference area. Blood from adults in the contaminated area averaged 475 +/- 200 and 125 +/- 34 ng/g wet weight for males and females, respectively. In the reference area, blood PCB concentrations were 7 +/- 3 and 4 +/- 1 ng/g wet weight for males and females, respectively. Significant positive relationships were found between carapace length and blood PCB concentration for both sexes in the contaminated area; however, only a marginal relationship was found between female carapace length and concentration of PCBs in their eggs. Our results suggest that PCB contamination of the upper Hudson River presents risks of establishing high body burdens and of maternal transfer of PCBs to eggs, although our measures of gross morphology revealed no discernable expression of abnormal sexual development or reproduction.

Polychlorinated biphenyl release from resuspended Hudson River sediment.

Three shear turbulence resuspension mesocosms (STORM tanks) were used to examine the release of polychlorinated biphenyls (PCBs) from resuspended Hudson River sediment. Twenty-two percent of the resuspended PCBs desorbed after 2 h, and 35% +/- 8% of PCBs were in the dissolved phase after apparent steady state was reached in 2 days. After the first resuspension event, the solids were allowed to settle and the quiescent time was varied to determine whether the labile pool of PCBs is recharged during sediment consolidation. The steady-state log Koc values for the third subsequent resuspension were higher than for the first event due to lower dissolved PCB concentrations; the particulate PCB concentrations were constant between events. With 1 day of consolidation between resuspension events, the dissolved concentration of all congeners decreased an average of 8% +/- 5% between subsequent resuspension events. With 4 days between events, only the dissolved pentachlorinated PCBs decreased significantly (p = 0.002), suggesting that the easily desorbable PCBs recharge when there is sufficient time between resuspension events.

Sources and distribution of polycyclic aromatic hydrocarbons in the sediments of Kaoping River and submarine canyon system, Taiwan.

In this study, we measured and analyzed polycyclic aromatic hydrocarbons (PAHs) in surface sediment samples collected from the Kaoping river and submarine canyon (KPSC) system to determine the compositional patterns and characteristic distributions of PAH and to elucidate the transport and fate of these land-derived particles. Concentrations of total PAH (sum of 28 PAH compounds) ranged from 22.6 to 45,100 ngg(-1) dry weight (dw) and the highest concentrations were found in the sediments of Donggang Harbor. The ratio of perylene to sum of penta-aromatic PAH isomers (47-55%) was higher in off-shore stations, suggesting a diagenetic PAH source. Various isomeric ratios also indicated that combustion was a significant source of PAH to the sediment at stations located along the Kaoping river and the north-western shelf of the Kaoping estuary. However, in the south-eastern shelf and some canyon sites, petroleum-derived PAHs were a more significant source of these compounds. Principal component analysis and hierarchical cluster analysis suggest PAHs in the sediments from the north-western shelf, and river and canyon sediments might be a pyrogenic product of coal and diesel-burning vehicles, while those of the south-eastern shelf may be petrogenic. PAH concentrations and compositional patterns are effective tracers of particulate transport in KPSC system. The seaward transport of riverine particulates was found to be mostly directed to NW-shelf and/or canyon.

Persistent organic pollutants in two dolphin species with focus on toxaphene and polybrominated diphenyl ethers.

Assessing trends of persistent organic pollutants (POPs) in marine mammals is difficult due to age, gender, and metabolism influences on accumulation. To help elucidate these effects in dolphins, POP concentrations were determined in the Atlantic white-sided dolphin, Lagenorhynchus acutus, a pelagic delphinid inhabiting North Atlantic waters, and in the rough-toothed dolphin, Steno bredanensis, a pelagic delphinid inhabiting tropical and subtropical waters. The specific objectives of this study were to determine baseline POP concentrations in L. acutus and S. bredanensis blubber samples and to examine the effects of age, gender, and metabolism on POP concentrations in dolphin blubber. Focus was aimed at contaminants of emerging concern, specifically, toxaphene and polybrominated diphenyl ethers (PBDEs). Samples collected from L. acutus (n = 47) stranding events in Massachusetts (1993--2000) and S. bredanensis samples (n = 15) were analyzed for PCBs, toxaphene, and other organic pesticides by gas chromatography/mass spectrometry (GC/MS). Age and gender influences were similar between the two species, with adult females having significantly lower POP concentrations as compared to adult males and juveniles. Mean sigma toxaphene concentrations were highest in juvenile L. acutus, 13.0 (6.7) microg/g wet mass (1 SD), and lowest in adult female S. bredanensis, 1.49 (1.4) microg/g wet mass. sigma PBDE (sum of congeners 47, 99, 100, 153, and 154) concentrations were highest in juvenile L. acutus, 2.41 (1.2) microg/g wet mass, and lowest in adult female S. bredanensis, 0.51 (0.6) microg/g wet mass. POP concentrations did not significantly differ between adult males and juveniles, suggesting metabolism of congeners and/or dilution with growth. PBDE concentrations in juvenile white-sided dolphins were not significantly related to collection year, suggesting that there may be a lag period for higher concentrations to be detected in pelagic marine mammals such as L. acutus or that concentrations have already peaked in this species prior to the first collection in 1993.

Dietary accumulation and metabolism of polybrominated diphenyl ethers by juvenile carp (Cyprinus carpio).

Polybrominated diphenyl ethers (PBDEs) are hydrophobic organic contaminants with properties and nomenclature similar to polychlorinated biphenyls (PCBs). While much information is available on the bioaccumulation and pharamcokinetics of PCBs, little information is available on PBDEs. In this study, juvenile carp were exposed to a diet spiked with a cocktail of four BDE congeners (2,4,4'-tribromoDE [BDE 28], 2,2',4,4'-tetrabromoDE [BDE 47], 2,2',4,4',5-pentabromoDE [BDE 99], and 2,2',4,4',5,5'hexabromoDE [BDE 153]) for 60 d followed by a 40-d depuration period. As a positive control, three PCB congeners with similar log K(ow), values (2,2',5,5'-tetrachlorobiphenyl [PCB 52], 2,2',4,4', 5,5'-hexachlorobiphenyl [PCB 153], and 2,2',3,4,4',5,5'-heptachlorobiphenyl [PCB 180]) were included in the cocktail to compare their assimilation and fate with the model BDE congeners. Concentrations of BDEs and PCBs were monitored in whole-fish tissues and liver tissues over the duration of the experiment. In addition, blood serum samples were taken and pooled among replicates to determine if any phenolic metabolites of BDE and PCBs were formed. Rapid assimilation of BDE 47 was observed relative to all other BDE and PCB congeners, whereas apparently no accumulation of BDE 99 occurred over the course of the experiment. Assimilation efficiencies for BDE 47 suggest that approximately 100% of the BDE 47 exposure was absorbed by carp tissues after 60 d. However, based on the time course of BDE 47 assimilation, it is improbable that all BDE 47 was assimilated; more likely, production of BDE 47 in carp tissues occurred as a result of debromination of higher-brominated compounds, possibly BDE 99. The net assimilation efficiencies of BDE 28 and BDE 153 were also apparently low (20 and 4%, respectively) relative to the three PCBs (40% assimilated) examined in this study. The low assimilation efficiency and high depuration rates for BDEs suggest a higher potential for biotransformation. While all three PCB compounds displayed very similar assimilation and depuration rates, three of the four BDE compounds displayed significantly different assimilation rates among BDE congeners and relative to the PCBs. This study suggests that BDEs have significantly different fate dynamics relative to PCBs in wild carp and likely other species of fish.

Seasonal and annual loads of hydrophobic organic contaminants from the Susquehanna River basin to the Chesapeake Bay.

Water from the Susquehanna River was collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyl (PCB) congeners to estimate seasonal and annual riverine loads to the Chesapeake Bay. Temporal variations in the chemical loads resulted from the large changes in the water flow rates and in the particle-associated contaminant concentrations. Concentrations of PCBs and PAHs in river particles (ng/g) were twice as great as those in the northern Chesapeake Bay, indicating that the Susquehanna River is an important source of these contaminants to the bay. The river carries a majority of its hydrophobic organic contaminants (HOCs) in the particulate phase. During periods of high flow, large amounts of suspended particles in the river result in elevated HOC levels and increased loadings of these contaminants to the bay. From 1997 to 1998, 60% of the total annual HOC loading occurred in the early spring coincident with high river flows. The total PCB and PAH annual loadings from the Susquehanna River to the Chesapeake Bay were 76 and 3160 kg/year, respectively and 75% of the loaded organic contaminants were in the particulate phase. Principal component analysis of PAH and PCB congener patterns in the particles reveals that the river suspended particles were dominated by autochthonous production in the summer and by resuspended sediment and watershed erosion during the winter and early spring.

Debromination of polybrominated diphenyl ether congeners BDE 99 and BDE 183 in the intestinal tract of the common carp (Cyprinus carpio).

Polybrominated diphenyl ether (PBDE) congener patterns in biota are often enriched in tetra-, penta-, and hexabrominated diphenyl ethers, which is believed to result from the use of the commercial "pentaBDE" formulation. However, our evidence suggests that debromination of PBDEs occurs within fish tissues leading to appreciable accumulation of less brominated congeners. This suggests that PBDE body burdens can reflect both direct uptake from exposure and debromination of more highly brominated congeners. We conducted two independent dietary exposure studies using the common carp (Cyprinus carpio) to trace the fate of 2,2',4,4',5-pentabromodiphenyl ether (BDE 99) and 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE 183) in fish tissues. Carp were fed food spiked with individual BDE congeners for 62 d, and depuration was monitored during the following 37 d. Significant debromination was observed, converting BDE 99 to 2,2',4,4'-tetrabromodiphenyl ether (BDE47) and BDE 183 to 2,2',4,4',5,6-hexabromodiphenyl ether (BDE 154) and another as yet unidentified hexa-BDE congener. The BDE 99 concentration rapidly declined from 400 +/- 40 ng/g ww in the food to 53 +/- 12 ng/g ww in the gut content material sampled 2.5 +/- 1 h following feeding. At least 9.5 +/- 0.8% of the BDE 99 mass in the gut was debrominated to BDE 47 and assimilated in carp tissues. In the BDE 183 exposure, approximately 17% of the BDE 183 mass was debrominated and accumulated in carp tissues in the form of two hexa-BDE congeners. In both exposure studies, the concentration of the exposure compound decreased significantly in the gut within 2.5 +/- 1 h following ingestion. This rapid decrease in the concentration of the BDE congeners could not be explained entirely by debromination to quantified products or fecal egestion. Reactions occurring within the gut transform BDE congeners to other products that may accumulate or be excreted. Further studies are needed to identify and determine the effects of these BDE metabolites.

Debromination of the flame retardant decabromodiphenyl ether by juvenile carp (Cyprinus carpio) following dietary exposure.

The congener 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE 209) is the primary component in a commonly used flame retardant known as decaBDE. This flame retardant constitutes approximately 80% of the world market demand for polybrominated diphenyl ethers (PBDEs). Because this compound is very hydrophobic (log K(ow) approximately 10), it has been suggested that BDE 209 has very low bioavailability, although debromination to more bioavailable metabolites has also been suggested to occur in fish tissues. In the present study, juvenile carp were exposed to BDE 209 amended food on a daily basis for 60 days, followed by a 40-day depuration period in which the fate of BDE 209 was monitored in whole fish and liver tissues separately. No net accumulation of BDE 209 was observed throughout the experiment despite an exposure concentration of 940 ng/day/fish. However, seven apparent debrominated products of BDE 209 accumulated in whole fish and liver tissues over the exposure period. These debrominated metabolites of BDE 209 were identified as penta- to octaBDEs using both GC/ECNI-MS and GC/HRMS. Using estimation methods for relative retention times of phenyl substitution patterns, we have identified possible structures for the hexa- and heptabromodiphenyl ethers identified in the carp tissues. Although exposure of carp to BDE 209 did not result in the accumulation of BDE 209 in carp tissues, our results indicate evidence of limited BDE 209 bioavailability from food in the form of lower brominated metabolites.