Accumulation of PCB congeners in nestling tree swallows (Tachycineta bicolor) on the Hudson River, New York

Tree swallows (Tachycineta bicolor) were used as a sentinel species to monitor the contamination and bioavailability of polychlorinated biphenyls (PCBs) in the Hudson River watershed. Several tree swallow nest box colonies around and downstream from Hudson Falls, NY, were studied. Tree swallow eggs, adults, and 5-, 10-, and 15-day-old nestlings were collected and analyzed for 103 PCB congeners. Emergent insects collected by net (primarily Odonata) or as a food bolus (primarily Diptera) taken from the mouths of adult tree swallows returning to the nest were analyzed in the same manner. Total PCB concentrations (wet weight) in eggs from two contaminated sites ranged from 9000 to 25,000 ng/g and accumulated to 32,000 and 96,000 ng/g in 15-day-old nestling at two contaminated sites. The congener patterns of PCBs in eggs, nestlings, and adults were compared to those found in emergent insects (Odonata and Diptera) using principal components analysis. The PCB patterns of the biota differed from that of Aroclor technical mixtures. PCB patterns in adult tree swallows were similar to those in eggs, while the patterns in dietary insects were similar to nestling tree swallows. Uptake rate constants were determined for tree swallow nestlings and compared between the two contaminated sites. The estimated PCB congener uptake rate constants were 0.008-0.02 d(-1) based on uptake in nestlings until day 15 post-hatch. The rate constants were comparable between the two study areas and may be used to predict nestling contamination at other locations. Our studies confirm the utility of nestling tree swallows to evaluate localized PCB contamination.     

Fluxes of polychlorinated biphenyls volatilizing from the Hudson River, New York measured using micrometeorological approaches

This study represents the first time that a micrometeorological technique, using turbulent transport measurements, has been used to determine the direction and magnitude of air-water exchange of polychlorinated biphenyls (PCBs). The study was conducted during July 2008 on the Hudson River estuary near the Tappan Zee Bridge, which is the site of some of the most serious PCB contamination in the world. Gas-phase ΣPCB concentrations measured at two heights above the water column averaged 1.1 ng m(-3), and concentrations were usually lower in the upper air sample, indicating net transport of PCBs from the water column to the air. Volatilization PCB fluxes were calculated using the modified Thornthwaite-Holzman equation. Values of friction velocity and atmospheric stability were calculated using the Aerodynamic Gradient and Eddy Correlation techniques. The PCB fluxes were corrected for changes in atmospheric stability using the atmospheric stability factor of water vapor (?(w)) calculated from empirical formulations which ranged from 1.0 to 3.2 (neutral to stable atmospheric boundary layer conditions). Vertical ΣPCB fluxes ranged from +0.5 μg m(-2) d (-1) to +13 μg m(-2) d (-1). Mono- through tri-homologues accounted for about half of ΣPCB fluxes, with tetra- through hexa-homologue accounting for the other half. This work demonstrates the utility of a micrometeorological approach to measuring the air-water exchange of organic contaminants.     

PCB loading from sediment in the Hudson River: congener signature analysis of pathways

The upper Hudson River (NY) was subjected to massive PCB contamination over a period of three decades. A large inventory of PCBs remains in contaminated sediments of the river, most notably in the Thompson Island Pool. During the summer, flow crossing the Thompson Island Pool exhibits a large and consistent PCB load gain. This load gain is not associated with scouring flows and is not accompanied by an increase in suspended solids. A variety of hypotheses have been proposed to explain this load gain, including flux of contaminated porewater and dissolution of unverified reservoirs of pure PCBs. A wealth of congener-specific PCB data is available for the site throughout the 1990s. Interpretation of the Thompson Island Pool load gain is facilitated by examination of the PCB congener signature of the gain and comparison to the signature of potential sources. This examination suggests that neither the flux of porewater nor the dissolution of unaltered Aroclors are the predominant source of the load gain. Instead, the congener signature is consistent with a mixed source consisting of porewater flux and non-scour flux of contaminated sediments. The non-scour sediment flux, which reaches a maximum in the beginning of the summer growing season, is likely driven by a variety of biological and anthropogenic processes, including bioturbation by benthic organisms, bioturbation by demersal fish, scour by propwash, mechanical scour by boats and floating debris in nearshore areas, and uprooting of macrophytes.     

Emissions of nitrous oxide (N2O) from a tidal, freshwater river, the Hudson River, New York

Rivers receive a significant fraction of the anthropogenic nitrogen applied to the world's watersheds. Environmental conditions in rivers should be conducive to the formation of N2O, and recent models suggest that rivers could constitute up to 25% of the anthropogenic contribution of N2O to the atmosphere. Few direct measurements exist, however, of N2O flux between rivers, especially large rivers, and the overlying atmosphere. We measured the concentration of N2O over a 2-year period in a large, tidal, freshwater river. We coupled these measurements with a physical model of gas exchange based on inert gas tracer additions to this river and computed the flux of N2O to the atmosphere. The tidal, freshwater Hudson River is persistently supersaturated in N2O with respect to the atmosphere, with average partial pressure of N2O (pN2O) of 0.58 muatm or about 185% of atmospheric equilibrium. At all times during a 2-year cycle and at all locations sampled along a 200 km stretch of the river, the river was a net source of N2O to the atmosphere. We estimate that the tidal, freshwater Hudson River contributes 0.056 g of N2O-N m(-2) to the atmosphere annually. Despite relatively high concentrations of NO3 in the Hudson River, the tidal, freshwater river is a minor source of N2O in comparison to other rivers for which estimates exist and to components of its own watershed. The river itself accounts for only 1.3% of the total N2O contribution to the atmosphere that occurs in the Hudson watershed.     

PCB congeners and dechlorination in sediments of Sheboygan River, Wisconsin, determined by matrix factorization

Nine sediment cores were collected from the Sheboygan River Inner Harbor, WI, and analyzed for polychlorinated biphenyl (PCB) congeners. Total PCBs ranged from approximately 0 to 161 mg/g. Positive matrix factorization (PMF) was applied to the PCB data setto determine source profiles. Two factors were determined to be significant. One factor resembled the original approximated PCB mixture of 50% Aroclor 1248 and 50% Aroclor 1254 and the other factor was a dechlorinated version of the mixture. An anaerobic dechlorination model was applied to the dechlorinated source profiles to quantify possible dechlorination pathways. It was found that dechlorination process H' provided the best fit for an individual process, and H' + M provides the best fit for combined processes. PMF source contributions, and plots of PCB concentration versus congener for individual samples, provide evidence of enhanced dechlorination at high concentrations (>40 ppm) and small amounts of dechlorination at low concentrations (<3 ppm). In addition, downward migration of lower chlorinated PCBs in core SR1a has occurred. Remediation dredging in the Upper Sheboygan River in 1989 and 1990 reintroduced PCBs to the water column and selective transport of PCB 18 is observed in core SR7.     

Effects of historic PCB exposures on the reproductive success of the Hudson River striped bass population

Scientists and regulatory agencies have expressed concern that exposures to polychlorinated biphenyls (PCBs) might be contributing to reductions in the abundance of fish populations exposed to these chemicals. The specific effects of concern involve impairment of fish reproduction, including both reduced egg production and decreased viability of eggs and larvae. We tested hypotheses concerning the effects of PCBs on fish populations using long-term data sets available for the striped bass population of the Hudson River, NY, a population that has long been a subject of regulatory concern because of potential effects of PCB exposures. The data sets examined include both measurements of PCB concentrations in adult female striped bass over the period from 1976 through 1997 and estimates of the numbers of striped bass eggs, larvae, and juveniles produced annually during this same period. We found strong correlations between estimates of the abundance of spawners and the number of eggs and larvae produced by those spawners and also between independent estimates of year-class strength derived from different sampling programs. However, we found no relationships between PCB exposure and any measure of striped bass abundance or reproduction. Although inconsistent with the expected effects of PCB exposures, trends in all measures of striped bass abundance and reproductive success were consistent with the expected effects of striped bass harvest restrictions that were imposed during the 1980s. Our results demonstrate a need for caution in inferring risks to populations in nature from effects observed in laboratory studies.     

Polybrominated diphenyl ethers (PBDEs) in biota representing different trophic levels of the Hudson River, New York: from 1999 to 2005

It has been hypothesized that a principal route of human exposure to polybrominated diphenyl ethers (PBDEs), used as flame retardants, is through fish consumption. Between 1999 and 2005 PBDE-47, -99, -100, -153, and -154 were analyzed in 3797 biological samples of 33 species of the Hudson River, New York. Approximately 98.4% of the samples contained PBDEs between 0.5 and 37 169 ng g(-1) lipid, with a median concentration of 772 ng g(-1) lipid. Yearly median sigmaPBDE concentrations fluctuated. Samples from river miles 112 and 153 contained higher sigmaPBDEs than those from other locations of the river. The 7-year median sigmaPBDE concentrations were the highest in large carnivorous fishes and the lowest in insects. The median abundance of congener PBDE-47 decreased from 80% to 63% with decreasing levels of sigmaPBDEs in the samples, while an increase from 2% to 23% was observed for PBDE-99. The median abundance of other congeners did not change with concentrations of sigmaPBDEs. Positive-, negative-, and no-correlation between sigmaPBDE concentrations and fish weight were observed for different species and for the same species from different locations of the river. The sources of PBDE contamination, diet, metabolic activity, and sediment chemistry might affect the levels of PBDEs in a fish.     

Statistical method to evaluate the occurrence of PCB transformations in river sediments with application to Hudson River data

Polychlorinated biphenyls (PCBs) were produced in the mid 1900s for industrial use. The term PCBs refers to 209 theoretically possible chlorinated compounds of the biphenyl molecule (congeners). The number and location of the chlorines govern both the environmental fate and toxicity of each congener. Changes in the distribution of congeners in river sediments can result from congener transformation and/or preferential congener transport. This study exploits the distribution of PCB congeners, specifically congeners that maintain a constant ratio relationship in the commercially manufactured PCB mixtures (Aroclors), to quantify the likelihood of congener distribution shifts in river sediment. By using relative abundances, the influence of total PCB bias is eliminated. Correlated congeners (tracker pairs) maintain a constant relative proportion in sequentially more-highly chlorinated Aroclors, thus there is no need to know the source contaminating Aroclors a priori. Using the Frame et al. database of Aroclor congener distributions, 276 pairs of correlated congeners, constructed from 95 individual congeners, are identified. A comparison study of Aroclors and Hudson River sediments included 218 of the 276 tracker pairs. Conclusive evidence of a shift in the congener proportions is found in 120 of the 218 cases, a much greater number than expected if no change in congener distribution had occurred.     

Field observation and modeling of dissolved fraction sediment-water exchange coefficients for PCBs in the Hudson River

Chemical fate and transport models that simulate sediment-water exchange of contaminants typically employ empirically determined sediment-water exchange coefficients for the dissolved fraction to describe the net effect of poorly understood mechanisms. This paper presents field-derived observations of the coefficient for 12 PCB congeners and two PCB mixtures in the Thompson Island Pool, Hudson River, and also presents an evaluation of a theoretical sediment-water exchange model. An extensive PCB data set was used to compute apparent coefficients for PCBs in the pool. Average exchange coefficients for the 12 congeners ranged from 2.6 to 18.8 cm/ day, and results showed a strong seasonal dependence. Peak coefficient values occurred in mid-May to early July, preceding peak water temperatures by 1 month and lagging the spring high-flow period. The coefficients increase with increasing partition coefficients, suggesting a dependence on congener properties. The large magnitude of the coefficients and the variation among the congeners is inconsistent with the pore-water molecular-diffusion transport process. A theory-based, mechanistic two-layer model reproduces the nonlinear relationship between the sediment-water exchange coefficients and partition coefficients. This model includes transfer through the mixed sediment layer by bioturbation and diffusion transfer through a water-side boundary layer governed by flow velocity. Results suggest that this algorithm can provide increased accuracyto future system-level fate and transport models for hydrophobic chemicals. The seasonal variation in the transfer coefficient appears to be a poorly understood interaction of physical and biological processes and merits further study.     

Levels and toxicokinetic behaviors of PCDD, PCDF, and coplanar PCB congeners in common cormorants from Lake Biwa, Japan

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (Co-PCBs) were determined in the liver and pectoral muscle of common cormorants (Phalacrocorax carbo) collected from Lake Biwa, Japan. To clarify the toxicokinetic behaviors and potential toxicities of these chemicals, the present study addresses life-stage- and tissue-specific accumulation of the congeners. Total 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were in the range of 360 to 50,000 pg/g lipid weight in the liver and 310 to 12,000 pg/g lipid weight in the pectoral muscle. Among congeners, for which toxic equivalency factors were assigned, PCB126, 2,3,4,7,8-P5CDF, and 1,2,3,7,8-P5CDD made a greater contribution to total TEQs in the liver. Hepatic concentrations of T4- to H6CDDs, P5- and H6CDFs, and Co-PCBs (except PCB77) significantly increased with growth of cormorants, leading to life-stage-related compositional changes. The concentration ratios of liver to pectoral muscle revealed preferential accumulation of higher chlorinated congeners in hepatic tissue. For most congeners, concentration ratios significantly increased with an increase in hepatic total TEQs, suggesting their concentration-dependent hepatic sequestration. These results imply the presence of hepatic binding protein(s) such as cytochrome P450, inducible by these chemicals, which mayfunction as a binding species different from aryl hydrocarbon receptor. On the basis of these results, we conclude that the toxicokinetic behavior of each congener is life-stage-, tissue-, and concentration-dependent. TEQs in wildlife populations exposed to multiple congeners with varying concentrations should be used with caution for risk assessment, even within a species.     

PCB congeners and dechlorination in sediments of Lake Hartwell, South Carolina, determined from cores collected in 1987 and 1998

Four sediment cores were collected from Lake Hartwell, SC, in 1987 and 1998 and analyzed for polychlorinated biphenyl (PCB) congeners. Total PCBs ranged from -0 to 58 microg/ g. Positive matrix factorization (PMF) was applied to the data sets to determine PCB source profiles. Two factors were determined for each data set. One factor resembled the original estimated PCB mixture of 80% Aroclor 1016 and 20% Aroclor 1254 and the other factor was a dechlorinated version of the mixture. Evidence of a dechlorination plateau is apparent from the PMF loading solutions because the dechlorinated congener profiles do not change from 1987 to 1998, butthe contribution to the profile from the dechlorinated factor increases from 73% (1987) to 87% (1998). PMF source contributions and plots of PCB concentration versus congener for individual samples provide evidence of enhanced dechlorination at high concentrations. After source apportionment an anaerobic dechlorination model was applied to the dechlorinated source profiles to quantify possible dechlorination pathways. It was found that dechlorination process M, extended to target biphenyl rings with up to six chlorines, provided the best fit for an individual process, and M + Q provides the best fit for combined processes, although M + LP also provides a similarfit. Process LP targets the higher chlorinated congeners and appears to dechlorinate PCBs in the sediments initially.     

Sources and dechlorination of polychlorinated biphenyl congeners in the sediments of Fox River, Wisconsin

Polychlorinated biphenyl (PCB) congeners were analyzed in eight deep, dated sediment cores collected from the immediate upstream and downstream of DePere dam in Fox River, Wisconsin. The average time span of the cores is about 100 yr, except for one core (FR-9) which is influenced by mixing or covers a short time period (2 yr). The total PCB concentrations have a range of 0.2-6.8 ppm for the upstream and 0.3-17.6 ppm for the downstream cores. The PCB data obtained from the sampling were analyzed as upstream and downstream data, using a factor analysis (FA) model with nonnegative constraints to identify PCB sources and congener patterns. The factor loadings obtained from the FA model were interpreted in terms of the presence of possible environmental degradation mechanisms. In addition, a recently developed model, which is used to identify and quantify possible pathways of anaerobic dechlorination of PCBs in the sediments, was validated on the basis of in situ data from the literature, and then applied to the congener patterns obtained from the FA model. The major PCB source to the Fox River sediments is identified as Aroclor 1242, for both the upstream and the downstream sediments. Loss of di- and trichlorobiphenyls (e.g., 2-4, 25-2) from the sediments suggests desorption from the sediments. On the other hand, observation of elevated amounts of certain congeners such as 24-3 and 25-3 indicates the presence of anaerobic dechlorination activity. The anaerobic dechlorination model demonstrates significant similarities between the Aroclor 1242 profile altered according to dechlorination processes Q (upstream) and H' (downstream) and the dominant congener patterns obtained from the FA model.     

Bioaccumulation of organochlorines in crows from an indian open waste dumping site: evidence for direct transfer of dioxin-like congeners from the contaminated soil

To assess the significance of waste dumping sites as a source of chemical contamination to ecosystems, we analyzed the residue levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and other organochlorines in the breast muscle of crows from a dumping site in the south of Chennai city, South India. Crows from the dumping site contained significantly higher total TEQs (60 +/- 27 pg/g lipid wt) than those from the reference sites (26 +/- 18 pg/g lipid wt). Especially, certain dioxin-like coplanar PCB congeners (Co-PCBs), such as CB-77 and CB-105, whose source is commercial PCBs,were significantly higher in crows from the dumping site than those from the reference sites. Profiles of PCDDs/DFs and Co-PCBs in crows from the dumping site were similar to those of soil at the same site, which was confirmed by principal component analysis. Furthermore, significant positive correlations were obtained between the congener-specific bioconcentration factors (BCFs) of PCDDs/DFs estimated from concentrations in crows and soil from the dumping site and the theoretical BCFs calculated from water-particle and lipid-water partitioning coefficients. On the other hand, the estimated BCFs had significant negative correlations with the molecular weight of PCDDs/DFs, indicating that molecular size limits their bioaccumulation. These results suggest that dioxin-like congeners in the soil of the dumping site were transferred directly to the crows through the ingestion of on-site garbage contaminated with soil, rather than through trophic transfer in the ecosystem. The present study provides insight into the ecological impacts of dumping sites.     

Differential accumulation of polychlorinated biphenyl congeners in the terrestrial food web of the Kalamazoo River Superfund site, Michigan

A series of field studies was conducted to determine the bioaccumulation of polychlorinated biphenyl (PCB) congeners in the terrestrial food web of the Kalamazoo River flood plain. Samples included colocated soils, native plants likely to be consumed by wildlife, several taxa of terrestrial invertebrates, small mammals, passerine bird eggs, nestlings, and adults, and great horned owl plasma and eggs. Mean concentrations of total PCBs in samples from the former Trowbridge impoundment were 6.5 mg/kg dry weight for soils and 0.023, 0.13, 1.3, 1.3, 1.6, and 8.2 mg/kg wet weight for plants, small herbivorous mammals, depurated earthworms, shrews, great horned owl eggs, and house wren eggs, respectively. Historical data from the Kalamazoo River have reported Aroclor-equivalent total PCB concentrations in the terrestrial food web; however, the degree of environmental weathering of the parent PCB mixtures was unknown. In this study, earthworms and composite samples of coleoptera exhibited PCB congener patterns that were similar to patterns in colocated soils. However, in plants, less chlorinated PCBs (e.g., mono-, di-, tri-, and tetrachlorinated biphenyls) were predominant, and in small mammals, there was a notable enrichment of PCBs 153, 180, 138, 118, and 99. In general, concentrations of PCBs were lower in most biota than in soil from the Kalamazoo River Area of Concern (KRAOC) although there was a modest biomagnification of PCBs from lower trophic level biota to highertrophic levels. As a consequence of environmental weathering of PCBs in the terrestrial food web of the KRAOC, the relative potency of the PCBs (expressed as mg TEQs/kg PCBs) decreased from soil to most biota. While there was a general trend, as expected, in which concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) increased with total PCBs, this relationship was rather poor (R2 = 0.13). Taken together, these data suggest that the differential accumulation of PCB congeners in the terrestrial food web can be explained by congener-specific differences in bioavailability from soil, exposure pathways, and metabolic potential of each of the food web components.     

Differential accumulation of polychlorinated biphenyl congeners in the aquatic food web at the Kalamazoo River Superfund site, Michigan

A series of field studies were conducted to gain a better understanding of the bioaccumulation and dynamics of polychlorinated biphenyl (PCB) congeners in the aquatic food web of the Kalamazoo River flood plain. Representative species of passerine birds, mammals, fish, aquatic plants, invertebrates, and colocated sediments were collected from areas located within submerged portions of the former Trowbridge impoundment and also from areas located at an upstream reference location. In most matrixes, total concentrations of PCBs were significantly greater in the downstream study area compared to the upstream reference location. Patterns of PCB congeners varied among trophic levels due to selective bioaccumulation of more chlorinated congeners in upper trophic level organisms. There were no statistically significant differences in total PCB concentrations among sampling grids within either site or temporally among three sampling seasons between May and September. The greatest total PCB concentrations were detected in adult tree swallows (mean = 8.7 mg/kg wet weight (ww)) and fish (mean = 4.4 mg/ kg ww) collected from the former Trowbridge impoundment. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) were greatest in egg, nestling, and adult tree swallows collected from the former Trowbridge impoundment. There was not a significant correlation between concentrations of total PCBs and TEQs at either site in the mammalian or avian food webs. The relative potency of the mixture of PCBs, expressed as the ratio of TEQs to total PCBs, increased with trophic position in the avian and mammalian aquatic food webs located within the former Trowbridge impoundment.     

Characterization of background concentrations in upper Manhattan, New York apartments for select contaminants identified in World Trade Center dust

Residential indoor concentration of asbestos, lead, synthetic vitreous fiber (SVF), crystalline silica, calcite, gypsum, dioxin, and polycyclic aromatic hydrocarbons (PAHs) were measured in 25 residences and 9 building-interior common areas in upper Manhattan, NY. This was done to characterize the background levels of contaminants, identified in dust related to the collapse of the World Trade Center towers, at locations that were minimally impacted by the dust fallout. The study was initiated due to the paucity of background concentrations on building-related materials and combustion byproducts in urban residential dwellings. Asbestos, lead, SVF, crystalline silica, and dioxin were detected at very low concentration at some locations, and many samples tested below their respective analysis detection limits. Almost all of the environmental samples for PAHs, calcite, gypsum, and certain other building materials tested below their respective analysis detection limits. A comparative analysis to the limited literature data showed general agreement with the values found in this study. This study provides insight into the levels of these contaminants in lower Manhattan residential buildings prior to the attack, and these data will serve to enhance the available database for characterizing indoor environments for these contaminants.