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.     

Abundances, depositional fluxes, and homologue patterns of polychlorinated biphenyls in dated sediment cores from the Pearl River Delta, China

Despite the recent efforts to investigate the distribution and fate of persistent organic pollutants in the tropical and subtropical regions of Asia, very little was known about the temporal change of polychlorinated biphenyls (PCBs) in the environmental ecosystem of China. In this study, three dated sediment cores collected from the Pearl River Delta of southern China were analyzed for a large suite of PCB congeners, from which the temporal profiles of PCB abundances, fluxes, and homologue patterns were constructed. The sedimentary inventories of total PCBs at the sampling sites ranged from 480 to 1310 ng/cm2, at the low end of the worldwide figures. Although production and use of PCBs have been banned or highly restricted in China since the early 1980s, the fluxes of total PCBs continued to increase in the Pearl River Delta sediments. There was a concurrent increase of PCB fluxes and gross domestic product per capita in the region from 1980 to 1997, and a decline of agricultural land use was evident at the same time. Apparently, large-scale land transform since the early 1980s as well as emissions from the PCB-containing electrical equipments were responsible for the sharp rise of PCB fluxes in the recent sediments. The difference in the PCB homologue patterns from 1940 to the mid-1970s was probably indicative of the different timelines of PCB usage in Macao/Hong Kong and mainland China and the differenttypes of technical PCBs commercially used. PCBs were detectable in sediments deposited well before the time frame when production of PCBs began (before 1930) and were relatively enriched in the less chlorinated homologue groups (3Cl and 4Cl PCBs), suggesting the downward mobility of lightly chlorinated PCB congeners in the sediment column.     

Reduction of congener specific PCBs in water and peanut oil by polyethylene packaging film

The use of polyethylene film to reduce the concentration of selected polychlorinated biphenyl (PCB) congeners (one each from tri to deca chlorinated) from aqueous and oil systems, was investigated. The trend in removal of PCBs from the aqueous system showed an inverted mirror pattern of its uptake by the polyethylene film. There appeared to be little loss of PCBs from the oil during the duration of the study. The rate loss from each system was compared as a function of PCB congener types. The results show that the lower chlorinated congeners were removed at a faster rate from the water than their higher counterparts. In the oil, the congeners with higher chlorination generally were removed at a faster rate than those with lower chlorination. The mass balance ratio confirmed that the PCBs removed from the dissolved solutions were sorbed by the contacting polyethylene film.     

Development and validation of protocols to differentiate PCB patterns between farmed and wild salmon

Polychlorinated biphenyl (PCB) congener patterns based on full congener PCB analyses of three farmed and five wild species of salmon from coastal British Columbia, Canada are compared using principal components analysis (PCA) and the best fit linear decomposition of the observed PCB composition in terms of Aroclor 1242, 1254, and 1260 end-members. The two complementary analysis methods are used to investigate congener composition pattern differences between species, trophic levels, feeding preferences, and farmed or wild feeding regimes, with the intent of better understanding PCB processes in both salmon and salmon consumers. PCA supports classification of PCB congeners into nine groups based on a) structure activity groups (SAG) related to the bioaccumulation potential in fish-eating mammals, b) Cl number, and c) the numbers of vicinal meta- and para-H. All three factors are needed to interpret congener distributions since SAGs by themselves do not fully explain PCB distributions. Farmed salmon exhibit very similar congener patterns that overlap the PCA and Aroclor composition of their food, while wild salmon separate into two distinct groups, with chinook and "coastal" coho having higher proportions of the higher chlorinated, Aroclor 1260 type, nonmetabolizable congeners, and chum, pink, sockeye, and "remote" coho having higher proportions of the lower chlorinated, more volatile and metabolizable Aroclor 1242 type, congeners. Wild chinook have the highest PCB and toxic equivalent (TEQ) concentrations, and the highest proportions of A1254 A1260, and PCB congeners in the most refractory SAG. Because both "coastal" and "remote" coho groups are likely to be consuming prey of similar size and trophic level, the PCB delivery mechanism (e.g., atmosphere vs runoff) apparently has more influence on the salmon PCB profile than biotransformation, suggesting that the wild chinook PCB profile is determined by feeding preference. Overall, wild salmon distributions primarily relate to trophic level, feeding preferences, and longevity, while metabolism appears at most a minor factor. The new classification protocol takes better advantage of individual congener PCB analyses and provides a better framework for understanding the PCB distributions in salmon and, potentially, the movement of individual PCB congeners through marine food chains than previous classification schemes.     

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.     

Latitudinal fractionation of polychlorinated biphenyls in surface seawater along a 62 degrees N-89 degrees N transect from the southern Norwegian Sea to the North Pole area

Surface seawater concentrations of PCBs, relative congener abundance, and possible effects of cold condensation were studied along a transect from the southern Norwegian Sea to the central Arctic Ocean (62 degrees N-89 degrees N). Large volume samples were collected from an ice breaker using a stainless steel surface seawater intake connected online to an ultra-clean laboratory. Concentrations of all studied PCB congeners, except for trichlorinated PCB 18, decreased with latitude. For instance, PCB 52 decreased from 470 fg L(-1) at 62 degrees N to 110 fg L(-1) at 89 degrees N and PCB 180 from 110 to 12 fg L(-1). Concentrations in the central Arctic Ocean were on the order of 10-100 fg L(-1) for the most abundant congeners. The relative contribution oftrichlorinated PCBs to the total PCB concentration increased with latitude, the tetrachlorinated contribution to the total PCBs did not show any correlation to latitude, and the relative contribution of heavier congeners decreased with latitude. This study establishes the occurrence at very low abundances of PCBs in seawater in the central Arctic Ocean and demonstrates a northward concentration decrease. The latitudinal shift in congener pattern is reflecting the relative propensity of the PCB congeners to undergo long-range transport in the Arctic and is consistent with their relative vapor pressures.     

Congener-specific tissue distribution of aroclor 1254 and a highly chlorinated environmental PCB mixture in rats

Polychlorinated biphenyl (PCB) mixtures were synthesized and marketed in Eastern European countries, but little is known abouttheir composition, distribution, ortoxicity. PCB-contaminated soil from the former production site of the Polish PCB mixture Chlorofen was collected, and the PCBs were extracted. An in vivo study was performed to investigate the PCB tissue distribution and biochemical effects of this soil extract in immature male Sprague-Dawley rats. Rats were administered 0.05 mmol/kg soil-extracted PCBs or Aroclor 1254 and sacrificed 7 days later, and congener-specific PCB profiles in selected tissues were determined. Distribution of SigmaPCBs (sum of 120 congeners) in tissues was primarily a function of lipid content of the tissues, except for the spleen, which retained more PCB than other tissues. Multivariate analysis of the PCB congener data showed that (a) congener profiles in tissues had changed, as compared to the parent mixture; (b) disposition and redistribution of individual congeners in vivo differed between both mixtures; and (c) more highly chlorinated congeners were retained in the spleens of both treatment groups. Differences in the induction of cytochrome P-450 1A and 2B subfamilies reflected the homologue composition of the respective mixtures and predict a different toxicity profile for Chlorofen than for Aroclor 1254.     

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.     

Polychlorinated biphenyls in salmon and salmon feed: global differences and bioaccumulation

Concentrations of 160 polychlorinated biphenyl (PCB) congeners or congener groups were determined in approximately 600 farmed Atlantic salmon from around the world and wild (ocean-caught) Pacific salmon from the Northeast Pacific. Concentrations and PCB congener profiles were analyzed to provide insight into the sources and uptake of PCBs in salmon as well as regional differences. Although total PCB concentrations in wild salmon appeared to be correlated to total lipid content, the increased proportion of total lipids in the farmed salmon could not account for the much greater PCB concentrations. We investigated the PCB congener patterns of hundreds of salmon samples using principal component analysis to further illuminate regional and species differences. Three major PCB patterns were observed, in most wild fish (except British Columbia and Oregon chinook), in farmed fish from the Atlantic, and in most farmed fish from the Pacific. The PCB congener profiles of farmed salmon often closely corresponded to a sample of commercial feed purchased in the same region, indicating that the feed is likely to be the major source of PCBs for farmed salmon. In such cases where PCB profiles in fish and feed were similar, a comparison of congener concentrations in fish and the feed showed that the majority of congeners, with some notable exceptions, were bioaccumulative to the same extent, irrespective of physical properties.     

Global accounting of PCBs in the continental shelf sediments

The recycling longevity of hydrophobic organic contaminants (HOCs) within the global environment is set by their permanent removal through processes such as degradation and burial in geological reservoirs. More than 90% of the global sediment burial of organic carbon (OC) occurs on the continental shelves, representing < 10% of the earth's ocean area. The propensity of HOCs to associate with organic matter, and the proximity of most population centers and thus presumed source areas to coastal regions, led us to investigate shelf sediments as a depository of significance for global HOC budgets. Here, the global inventory and burial fluxes of polychlorinated biphenyls (PCBs) in continental shelf sediments were estimated on a congener-specific basis from a database of 4214 distinct continental shelf surface sediment samples. To account for near-urban sampling bias, the locations of each datum relative to nearest population center were classified as Local (< 1 km), Regional (1-10 km), or Remote (> 10 km), according to a comprehensive vector map of the world (Digital Chart of the World) in a GIS environment. The global inventory of, for instance, PCB congener 153 was 1200 ton (95% confidence limit maximum: 2100 ton; and minimum 720 ton). The Remote sub-basin of the North Atlantic contains approximately half of the global shelf sediment inventory for most of the PCB congeners studied. The shelf sediment inventories of individual PCB congeners constitute significant fractions of their recently updated cumulative historical global emissions estimates. The estimated inventory in the shelf corresponds to about 10% of maximum emission estimates for lower-chlorinated congeners. However, for the more bioaccumulable, higher-chlorinated, congeners the shelf reservoirs appear to account for up to 80% of the estimated maximum cumulative global emissions. These shelf inventories represent 1-6% of the global industrial production of PCBs. The global burial fluxes were estimated to be on the order of 8-24 ton/yr each for the eight major congeners investigated, again, with the shelf constituting a more significant removal sink of the more chlorinated congeners. The permanent removal into deeper shelf sediments of PCB153 and PCB180 suggests that the global environmental mean residence times of these pollutants are on the order of 110 and 70 years, respectively. Hence, even after production and direct releases have been halted, we may expect to be exposed to such persistent pollutants for decades and centuries to come.     

Long-term recovery of PCB-contaminated sediments at the Lake Hartwell superfund site: PCB dechlorination. 1. End-member characterization

Under anaerobic conditions, such as those typically found in buried sediments, the primary metabolic pathway for polychlorinated biphenyls (PCBs) is reductive dechlorination in which chlorine removal and substitution with hydrogen by bacteria result in a reduced organic compound with fewer chlorines. Vertical sediment cores were collected from Lake Hartwell (Pickens County, SC) and analyzed in 5-cm intervals for 107 PCB congeners in a total of more than 280 samples from 18 sediment cores and surface samples. This paper reports on extensive PCB dechlorination measured in Lake Hartwell sediments and the characterization of dechlorination end-member (EM) patterns using chemical forensic methods. PCB congener fingerprinting and a multivariate receptor modeling method, polytopic vector analysis (PVA), were used for identification and characterization of weathered and dechlorinated PCB congener patterns. Dechlorination resulted in a substantial shift in buried sediments from tetra- through decachlorobiphenyl congeners to mono- through trichlorobiphenyl congeners. Mono- through trichlorobiphenyls comprised approximately 80% of the PCBs in buried sediments that underwent maximum dechlorination as compared to approximately 20% in surface sediments. The major concentration decreases were seen in the tetra- through hexachlorobiphenyl homologues, which accounted for over 90% of the dechlorination. Octa- through decachlorobiphenyl congeners also were dechlorinated, but their overall contribution to dechlorination was relatively small due to their low initial concentrations (< 5%). The net accumulation of 2-CB, 2,2'/2,6-DCBs, 2,4'-DCB, 2,2',4-TCB, and 2,2',6-TCB at Lake Hartwell matched characteristic PCB dechlorination products reported in the literature, such as those for Processes M, Q, and C; and the persistence of tetrachlorobiphenyls (TeCBs) that contained 24- and 25-congener groups resembled dechlorination Processes H or H'. Although dechlorination tended to be very extensive in most of the cores, it was not always consistent from core to core or at various depth intervals within a single core. The reason for this variability in dechlorination extent could not be determined from the existing data and did not appear to correlate with such factors as PCB concentration, total organic carbon, or age. The authors used fingerprinting analysis and a PVA multivariate receptor model as exploratory data analysis tools to characterize PCB sources and their alteration patterns. Dominant sources and alteration patterns were determined in this large data set by comparing PVA EM patterns with known source patterns (i.e., Aroclors or Aroclor mixtures) and literature-reported alteration patterns. PVA also afforded an opportunity to characterize the vertical and lateral distributions of the weathered and unweathered PCB source patterns and dechlorination patterns, a task that would have been much more difficult to accomplish through comparison of chromatograms alone.     

PCB congeners in Lake Michigan coho (Oncorhynchus kisutch) and chinook (Oncorhynchus tshawytscha) salmon

We determined PCB congener concentrations in coho and chinook salmon collected in two Lake Michigan tributaries during the fall of 1996. Chinook salmon were larger than coho salmon and contained higher concentrations of the 78 PCB congeners we detected. There were no differences between male and female chinook or coho salmon in size or their PCB concentrations. Among individual fish, we found little evidence for a relationship between congener concentrations and percent lipid; however, congener concentrations did show a generally positive relationship with salmon size. Fish and macroinvertebrate congener concentrations are clearly related, and PCB congeners biomagnify approximately 20-30-fold as they flow from macroinvertebrates, two trophic levels below salmon, to the salmon. Slopes of regressions of salmonid congener concentrations on macroinvertebrate congener concentrations within homologs indicated that the degree of biomagnification generally increased with the degree of congener chlorination, although this pattern was much stronger for Mysis than for Diporeia. Log Kow and categorical variables for coplanar and "toxic" PCBs were not significant additional model terms, indicating that bioaccumulation of PCB congeners was not statistically related to these physicochemical attributes of the PCBs. The distribution of homologue PCBs shifts from a distinct predominance of hexachlorobiphenyls in macroinvertebrates to pentachlorobiphenyls and hexachlorobiphenyls in the salmon.     

Polychlorinated biphenyls in nonaccumulating, century-old sediments: sources, signatures, and mechanism of introduction

This study documents the occurrence of highly chlorinated PCB congeners in stream sediment deposited over 100 years ago. Penta- to heptachlorinated congeners (> 80%) have been found at concentrations up to 78.8 ng/g (dw) in core samples of a small, rural tributary of Lake Ontario. Lower chlorinated congeners and other organochlorine compounds occur sporadically; 210Pb and 137Cs are lacking. The most plausible mechanism is accumulation of dissolved-phase PCBs in permeable sediments adjacent to the creek channel. The similarity between core and air samples collected in the drainage basin suggests derivation from a residual fraction of atmospherically derived PCB congeners.     

Snapping turtles (Chelydra serpentina) as bioindicators in Canadian areas of concern in the Great Lakes Basin. 1. Polybrominated diphenyl ethers, polychlorinated biphenyls, and organochlorine pesticides in eggs

We examined the concentrations and spatial patterns of congeners of PBDEs, PCBs, and organochlorine pesticides in snapping turtle (Chelydra serpentina) eggs from Areas of Concern (AOCs) on the Canadian shores of Lake Ontario, St. Lawrence River, and connecting channels. Eggs from Lyons Creek (Niagara River AOC) reflected a local PCB source over a range of 7.5 km (3.2-10.8) from the Welland Canal. PCB contamination in eggs declined with increasing distance from the Welland Canal, whereas the relative contribution of congeners associated with Aroclor 1248/1254 increased with sigma PCB concentrations. Compared to turtle eggs from other sites in Lake Erie and Lake Ontario, eggs from Lyons Creek and Snye Marsh had PCB congener patterns that reflected a strong contribution from Aroclor 1254. PCBs in the eggs were associated with industrial sources and reflected the composition of different Aroclor technical mixtures. Organochlorine pesticides in eggs tended to be highest at Hamilton Harbour and Bay of Quinte AOCs, and were dominated by DDE, sigma chlordane, and mirex. In contrast, PBDE congener patterns in turtle eggs resembled PentaBDE technical formulations regardless of absolute concentrations or location, and were largely associated with urban environments.     

The absorption and translocation of polychlorinated biphenyl congeners by Cucurbita pepo ssp pepo

The mobility of polychlorinated biphenyl (PCB) congeners within Cucurbita pepo ssp pepo cv. Howden (pumpkin), a PCB phytoextracting plant, was investigated through a comparison of field-weathered soil, root, shoot, and xylem sap congener profiles. This is the first study to show the presence of PCBs in xylem sap (range: 0.03-0.18 μg·mL(-1)), confirming that PCB translocation throughout the plant occurs via this medium. A comparison of soil (5.2 ± 2.5 μg·g(-1)), root (27.1 ± 2.1 μg·g(-1)), shoot (range: 1.9 ± 0.5 μg·g(-1) - 8.2 ± 1.4 μg·g(-1)), and xylem sap (0.09 ± 0.04 μg·g(-1)) samples showed significant differences in congener profiles, with lower chlorinated congeners (predominately trichlorinated ones) found within xylem sap in higher amounts than higher chlorinated congeners. The total PCB concentrations of xylem sap samples collected at various lengths along the primary plant shoot were not significantly different from each other, while those of primary shoot tissue samples significantly decreased (two-sample t test, p = 0.01) as the distance from the plant base increased. PCA analysis of individual congeners in the roots, shoots and xylem sap indicated that movement of the PCB congeners in the plant was affected by the number of chlorines in the molecule, and hence possibly log K(ow) and molecular weight, but not by planarity.     

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.     

Partitioning and bioaccumulation of PBDEs and PCBs in Lake Michigan

Water from Lake Michigan and fish from all five Great Lakes have been sampled and analyzed for a suite of six polybrominated diphenyl ether (PBDE) congeners and 110 polychlorinated biphenyl congeners (PCBs). The Lake Michigan dissolved phase PBDE congener concentrations (0.2 to 10 pg/L) are similar to dissolved phase PCB congener concentrations (nondetected to 13 pg/L). Partitioning of PBDEs between the particulate and dissolved phases exhibits behavior similar to that of PCBs. Organic-carbon-normalized water-particle partition coefficients (log K(OC)s) ranged from 6.2 to 6.5. Lake trout are depleted in BDE-99 relative to dissolved phase concentrations, and in contrast to what is expected from the PCB congener patterns. This reflects suspected debromination of BDE-99 in the food web of Lake Michigan. A regression of the log of the bioaccumulation factor (BAF) and the log of the octanol-water partition coefficent (K(OW)) indicated a positive relationship for both PCB congeners and PBDE congeners. BDE-99 does not appear to followthe same trend, a further indication that it is subject to biotransformation. Using the PBDE BAFs for Lake Michigan and the PBDE fish concentrations from the other Great Lakes it is expected that the dissolved phase concentrations of congeners in the other lakes would range from 0.04 to approximately 3 pg/L.     

Congener-specific analysis of Pcbs in food samples by using GC/MS

A GC/MS method for congener-specific analysis of polychlorinated biphenyls (PCBs) in food samples was evaluated. There was good agreement between total concentration of PCBs in fish samples (n = 16) measured by using the GC/MS method and the conventional GC-ECD method. The total diet study samples (fishery food, meat, egg, milk, and their products) collected from Osaka in 1982-2001 were analyzed by using the GC/MS method to estimate the temporal trend of daily intake of PCBs from food. The estimated daily intake of total PCBs (sum of tri- to heptaCBs) was in the range of 0.7-4.4 microg/person/day, far below the Japanese provisional acceptable daily intake (250 microg/50 kg-person/day). The dominant congener was 2,2',4,4',5,5'-hexachlorobiphenyl (#153), which accounted for 9-15% of total PCB. The ratio of lower chlorinated congeners decreased from the 1980's to post-2000. The results indicate that the PCB congener profile in foods has gradually changed.     

Assessment of natural attenuation via in situ reductive dechlorination of polychlorinated biphenyls in sediments of the Twelve Mile Creek arm of Lake Hartwell, SC

Polychlorinated biphenyl (PCB)-contaminated sediment cores taken from five locations in Lake Hartwell, SC, with an increasing distance from the point source were evaluated for the presence of in situ reductive dechlorination of PCBs on the basis of a comparative congener-specific analysis of PCB distribution profiles between historical (1987) and current (1998) sediments from the same sites. A layer of 1998 sediment that was equivalent to 1987 sediment was determined by direct comparison of total PCB depth profiles after correction for any sedimentation that occurred at each location since 1987. Natural capping of contaminated sediments with the continued deposition of new sediments was observed in all locations except the one farthest from the source area. The residual PCB congeners accumulated in the field samples did not vary from site to site. Certain PCB congeners (e.g., 236-24 + 34-34, 245-25, and 23-4 CB) decreased with time and with depth along with an increase in lower chlorinated PCB congeners in all sampling locations. A similarity in distribution profiles between dechlorinated PCBs in laboratory microcosms and in the field samples was observed. These results provide supporting evidence that in situ reductive dechlorination has occurred in the Twelve Mile Creek arm of Lake Hartwell. Several sediment layers, particularlythe sites with highest PCB concentration, showed similar PCB distribution profiles between 1987 and 1998. An additional change in chlorine distribution between 1987 and 1998 at most "equivalent" depths was not observed. The ortho- and para-substituted congeners that accumulated during dechlorination of Aroclor 1254 after nearly 1 yr of incubation in the laboratory were the prominent residual products in all field samples. At a few locations and depths, evidence for dechlorination at surprisingly low concentrations (1-5 ppm) was observed. These results confirm that in situ reductive dechlorination of PCBs is operating at a very slow rate and may have been at a plateau since 1987 for certain depths and certain locations.     

Identifying sources and biomagnification of persistent organic contaminants in biota from mountain streams of southwestern British Columbia, Canada

We assessed whether biota occupying mountain streams accumulate and biomagnify remotely derived organic pollutants originating from atmospheric inputs to snowpack and glacial runoff and from marine sources introduced by migrating anadromous salmon. Several persistent organic pollutants including polychlorinated biphenyls (PCBs), p,p'-dichloro-diphenyl-dichloroethylene, hexachlorobenzene, and trans-nonachlor were commonly detected in benthic invertebrates, salmon fry (Oncorhynchus spp.), and eggs of an aquatic passerine, the American dipper (Cinclus mexicanus) from the Chilliwack River watershed, British Columbia, Canada. Total PCBs and several organochlorines (OCs) biomagnified from benthic invertebrate composites to salmon fry to dipper eggs. Invertebrate samples generally did not differ significantly in contaminant burdens between the river main stem where salmon are more abundant and higher-elevation tributaries where the salmon density is lower. Concentrations of total OCs and total PCBs in dipper eggs were positively related to drainage basin area and collection year but not to elevation. No differences in PCB congener patterns existed between dipper egg samples from the Chilliwack watershed and other watersheds in southwestern British Columbia. However, principal component analysis revealed significant spatial differences in egg PCB congener patterns between the main Chilliwack River and the higher-elevation tributaries. This difference was primarily due to a greater occurrence of lower chlorinated PCB congeners (66 and 105) in dipper eggs collected from the tributaries and higher loadings of the more stable and persistent congeners (153, 138, 130, and 128) in eggs from the river main stem. The results suggest that atmospheric sources are the main contributor of contaminants detected in biota from the region and that biomagnification is a common pathway for accumulation in lotic predators such as the American dipper.