Addition of carbon sorbents to reduce PCB and PAH bioavailability in marine sediments: physicochemical tests

The addition of activated carbon as particulate sorbent to the biologically active layer of contaminated sediment is proposed as an in-situ treatment method to reduce the chemical and biological availability of hydrophobic organic contaminants (HOCs) such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We report results from physicochemical experiments that assess this concept. PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay, CA, was contacted with coke and activated carbon for periods of 1 and 6 months. Sediment treated with 3.4 wt % activated carbon showed 92% and 84% reductions in aqueous equilibrium PCB and PAH concentrations, 77% and 83% reductions in PCB and PAH uptake by semipermeable membrane devices (SPMD), respectively, and reductions in PCB flux to overlying water in quiescent systems up to 89%. Adding coke to contaminated sediment did not significantly decrease aqueous equilibrium PCB concentrations nor PCB or PAH availability in SPMD measurements. Coke decreased PAH aqueous equilibrium concentrations by 38-64% depending on coke dose and particle size. The greater effectiveness of activated carbon as compared to coke is attributed to its much greater specific surface area and a pore structure favorable for binding contaminants. The results from the physicochemical tests suggest that adding activated carbon to contaminated field sediment reduces HOC availability to the aqueous phase. The benefit is manifested relatively quickly under optimum contact conditions and improves in effectiveness with contact time from 1 to 6 months. Activated carbon application is a potentially attractive method for in-situ, nonremoval treatment of marine sediment contaminated with HOCs.     

Field-scale reduction of PCB bioavailability with activated carbon amendment to river sediments

Remediation of contaminated sediments remains a technological challenge because traditional approaches do not always achieve risk reduction goals for human health and ecosystem protection and can even be destructive for natural resources. Recent work has shown that uptake of persistent organic pollutants such as polychlorinated biphenyls (PCBs) in the food web is strongly influenced by the nature of contaminant binding, especially to black carbon surfaces in sediments. We demonstrate for the first time in a contaminated river that application of activated carbon to sediments in the field reduces biouptake of PCBs in benthic organisms. After treatment with activated carbon applied at a dose similar to the native organic carbon of sediment, bioaccumulation in freshwater oligochaete worms was reduced compared to preamendment conditions by 69 to 99%, and concentrations of PCBs in water at equilibrium with the sediment were reduced by greater than 93% at all treatment sites for up to three years of monitoring. By comparing measured reductions in bioaccumulation of tetra- and penta-chlorinated PCB congeners resulting from field application of activated carbon to a laboratory study where PCBs were preloaded onto activated carbon, it is evident that equilibrium sorption had not been achieved in the field. Although other remedies may be appropriate for some highly contaminated sites, we show through this pilot study that PCB exposure from moderately contaminated river sediments may be managed effectively through activated carbon amendment in sediments.     

Biodynamic modeling of PCB uptake by Macoma balthica and Corbicula fluminea from sediment amended with activated carbon

Activated carbon amendment was assessed in the laboratory as a remediation strategy for freshwater sediment contaminated with polychlorinated biphenyls (PCBs) from the Grasse River (near Massena, NY). Three end points were evaluated: aqueous equilibrium PCB concentration, uptake into semipermeable membrane devices (SPMDs), and 28-day bioaccumulation in the clam Corbicula fluminea. PCB uptake by water, SPMDs, and clams followed similar trends, with reductions increasing as a function of carbon dose. Average percent reductions in clam tissue PCBs were 67, 86, and 95% for activated carbon doses of 0.7, 1.3, and 2.5% dry wt, respectively. A biodynamic model that incorporates sediment geochemistry and dietary and aqueous uptake routes was found to agree well with observed uptake by C. fluminea in our laboratory test systems. Results from this study were compared to 28-day bioaccumulation experiments involving PCB-contaminated sediment from Hunters Point Naval Shipyard (San Francisco Bay, CA) and the clam Macoma balthica. Due to differences in feeding strategy, M. balthica deposit-feeds whereas C. fluminea filter-feeds, the relative importance of the aqueous uptake route is predicted to be much higher for C. fluminea than for M. balthica. Whereas M. balthica takes up approximately 90% of its body burden through sediment ingestion, C. fluminea only accumulates approximately 45% via this route. In both cases, results strongly suggest that it is the mass transfer of PCBs from native sediment to added carbon particles, not merely reductions in aqueous PCB concentrations, that effectively reduces PCB bioavailability and uptake by sediment-dwelling organisms.     

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.     

PCB bioavailability control in Lumbriculus variegatus through different modes of activated carbon addition to sediments

PCB bioavailability to a freshwater oligochaete (Lumbriculus variegatus) was studied using sediments from a PCB-impacted river that was treated with different modes of granular activated carbon (GAC) addition. For sedimenttreated with 2.6% GAC and mixed for 2 min prior to L. variegatus addition, the reduction in total PCB biouptake was 70% for 75-300 microm size carbon, and 92% for the 45-180 microm size carbon. For the case where the GAC was placed as a thin layer on top of the sediments without mixing, the reduction in total PCB uptake was 70%. PCB biouptake kinetics study using treated and untreated sediment showed that the maximum PCB uptake in tissue was achieved at 28 days and decreased after that time. Although the absolute uptake of PCB changed over time, the percent reduction in total PCB uptake upon GAC amendment remained constant after the first few days. Our results indicated that PCB bioavailability was reduced upon the addition and little or no mixing of GAC into sediments. PCB aqueous equilibrium concentration and desorption rates were greatly reduced after GAC amendment, indicating reductions in the two primary mechanisms of PCB bioavailability in sediments: chemical activity and chemical accessibility.     

Uptake of sediment-bound bioavailable polychlorobiphenyls by benthivorous carp (Cyprinus carpio)

It is unclear whether accumulation of sediment-bound chemicals in benthivorous fish depends on the degree of sequestration in the sediment like it does for invertebrates. Here, we report on the potential of slow and fast desorbing sediment-bound polychlorobiphenyl (PCB) fractions for accumulation in carp (Cyprinus carpio) in lake enclosures treated with different nutrient doses. Routes of PCB uptake were quantitatively evaluated for 15 PCBs (log Kow range 5.6-7.8) using model analysis. Fast-desorbing PCB fractions in the sediment were defined as the ratio of 6-h Tenax-extractable to (total) Soxhlet-extractable concentrations. These fractions varied between 4 and 22% and did not show a clear trend with log Kow. However, bioaccumulation of PCBs in carp correlated much better with Tenax-extractable concentrations than with total-extractable concentrations. Nutrient additions in the enclosures had a positive effect on PCB accumulation. Model results showthat PCB uptake in carp can be explained from (1) uptake through invertebrate food, (2) uptake from fast-desorbing fractions in ingested sediments, and (3) uptake from water, where PCBs are in partitioning equilibrium with fast-desorbing fractions. The main implication of this research is that fast-desorbing PCB fractions in sediments have great predictive potential for bioaccumulation in benthivorous fish.     

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.     

Concentrations and fluxes of salmon-derived polychlorinated biphenyls (PCBs) in lake sediments

Fourteen sediment cores were collected from 10 lakes spanning a large gradient of sockeye salmon returns (0-40 000 spawners km(-2)) in Alaska and British Columbia in 1995-98 and 2002/03. The cores were analyzed for 210Pb to determine sedimentation rates and focusing factors. Polychlorinated biphenyl (PCBs) concentrations in the surface sediments (0-2 cm) were highly correlated with the number of sockeye salmon returns to each nursery lake. For 2002/03, the correlation between PCB concentration and number of salmon spawners was best with no correction factors applied, but decreased considerably when corrected for sedimentation rates, and was improved again by correcting for sediment focusing. Although sigmaPCB concentrations were similar in 1995-98 and 2002/03, the congener patterns varied. Because salmon are the dominant source of PCBs for most of these lakes, variation in sediment congener pattern likely derives from variation in congener patterns carried by the salmon. Overall, total PCB input by salmon has remained relatively constant since 1995. Unlike temperate Great Lakes contaminant studies, the North American west-coast lakes dominated by salmon bio-transport showed no sign of recent decrease in PCBs.     

Enhanced reductive dechlorination of polychlorinated biphenyl impacted sediment by bioaugmentation with a dehalorespiring bacterium

Anaerobic reductive dehalogenation of commercial PCBs such as Aroclor 1260 has a critical role of transforming highly chlorinated congeners to less chlorinated congeners that are then susceptible to aerobic degradation. The efficacy of bioaugmentation with the dehalorespiring bacterium Dehalobium chlorocoercia DF1 was tested in 2-L laboratory mesocosms containing sediment contaminated with weathered Aroclor 1260 (1.3 ppm) from Baltimore Harbor, MD. Total penta- and higher chlorinated PCBs decreased by approximately 56% (by mass) in bioaugmented mesocosms after 120 days compared with no activity observed in unamended controls. Bioaugmentation with DF-1 enhanced the dechlorination of doubly flanked chlorines and stimulated the dechlorination of single flanked chlorines as a result of an apparent synergistic effect on the indigenous population. Addition of granulated activated carbon had a slight stimulatory effect indicating that anaerobic reductive dechlorination of PCBs at low concentrations was not inhibited by a high background of inorganic carbon that could affect bioavailability. The total number of dehalorespiring bacteria was reduced by approximately half after 60 days. However, a steady state level was maintained that was greater than the indigenous population of putative dehalorespiring bacteria in untreated sediments and DF1 was maintained within the indigenous population after 120 days. The results of this study demonstrate that bioaugmentation with dehalorespiring bacteria has a stimulatory effect on the dechlorination of weathered PCBs and supports the feasibility of using in situ bioaugmentation as an environmentally less invasive and lower cost alternate to dredging for treatment of PCB impacted sediments.     

Field deployment of polyethylene devices to measure PCB concentrations in pore water of contaminated sediment

Sediment pore water concentrations of polychlorinated biphenyls (PCBs) in a contaminated mudflat in San Francisco Bay, CA were determined by field-deployed polyethylene devices (PEDs). Sequential sampling of PEDs deployed in the field showed large differences in uptake rates and time to equilibrium compared to PEDs mixed with field-collected sediment in the laboratory. We demonstrate a modeling approach that involves the use of impregnated performance reference compounds (PRCs) and interpretation of the data either by PCB molar volume adjustment or environmental adjustment factors to measure pore water concentrations of 118 PCB congeners. Both adjustment methods predicted comparable sampling rates, and PCB pore water concentrations estimated by use of the molar volume adjustment method were similar to values analytically measured in pore waters from the laboratory and field. The utility of PEDs for sampling pore water in the field was evaluated at a tidal mudflat amended with activated carbon to sequester PCBs. Pore water concentrations decreased up to 60% within 18 months after activated carbon amendment, as compared to a mechanical-mixed control plot Results of this study illustrate PEDs provide an inexpensive, in situ method to measure total PCB contamination in sediment pore water using a small set of PRCs.     

PCB and PAH speciation among particle types in contaminated harbor sediments and effects on PAH bioavailability

This research provides particle-scale understanding of PCB and PAH distribution in sediments obtained from three urban locations in the United States: Hunters Point, CA; Milwaukee Harbor, WI; and Harbor Point, NY. The sediments comprised mineral grains (primarily sand, silt, and clays) and carbonaceous particles (primarily coal, coke, charcoal, pitch, cenospheres, and wood). The carbonaceous sediment fractions were separated from the mineral fractions based on their lower density and were identified by petrographic analysis. In all three sediments, carbonaceous particles contributed 5-7% of the total mass and 60-90% of the PCBs and PAHs. The production of carbonaceous particles is not known to be associated with PCB contamination, and it is very unlikely that these particles can be the source of PCBs in the environment Thus, it appears that carbonaceous particles preferentially accumulate PCBs acting as sorbents in the aqueous environment if PCBs are released directly to the sediment or if deposited as airborne soot particles. Aerobic bioslurry treatment resulted in negligible PAH loss from the carbonaceous coal-derived material in Milwaukee Harbor sediment but resulted in 80% of the PAHs being removed from carbonaceous particles in Harbor Point sediment. Microscale PAH extraction and analysis revealed that PAHs in Harbor Point sediment were associated mainly with coal tar pitch residue. PAHs present in semisolid coal tar pitch are more bioavailable than PAHs sorbed on carbonaceous particles such as coal, coke, charcoal, and cenosphere. Results of this study illustrate the importance of understanding particle-scale association of hydrophobic organic contaminants for explaining bioavailability differences among sediments.     

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.     

Source apportionment of polychlorinated biphenyls in the tidal Delaware River

The Delaware River, similar to many surface water bodies throughout the United States, is impaired due to polychlorinated biphenyl (PCB) concentrations that exceed the federal water quality standard. A total maximum daily load (TMDL) for PCBs in the Delaware was promulgated in 2003 after construction of a detailed water quality model that relied upon estimated PCB loadings from sources such as wastewater treatment plant effluents, contaminated sites, and tributaries. The purpose of this project was to corroborate this loading estimate by analyzing ambient water column data on PCB concentrations in the Delaware River via positive matrix factorization (PMF) in order to identify covarying congener patterns that are, in theory, associated with sources. The PMF program identified six factors (covarying congener patterns) that appear to be associated with sources, such as sediment resuspension, contaminated sites, and wastewater effluents and combined sewer overflows (CSOs). PCB 11 was found to be a useful tracer for CSO/ wastewater inputs despite the fact that no known dye manufacturers exist in the watershed. This analysis generally corroborates the PCB loading estimate used in the water quality model.     

Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes

Ecological factors may play an important role in the bioaccumulation of polychlorobiphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Geochemical and bioaccumulation behavior of these chemicals also appears to be related to the presence of black carbon (BC) in sediment. In situ PCB and PAH biota to sediment accumulation factors (BSAF) for benthic invertebrates, as well as 6h Tenax-extractable (fast-desorbing) concentrations and lake characteristics (including BC in sediment), were determined for different seasons in chemically similar but ecologically different lakes (fish-dominated turbid, algae-dominated turbid, and macrophyte-dominated). BSAFs could be explained with a model including a term for Freundlich sorption to BC and a term for uptake from fast-desorbing concentrations in ingested sediments. Freundlich coefficients for in situ sorption to BC (KF) were calculated from slow desorbing fractions and BC contents and agreed well with literature values for KF. Furthermore, in contrast to BSAFs based on total extracted concentrations, Tenax-based BSAF showed a strong positive correlation with log Kow. We therefore argue that BC caused slow desorption and limited BSAFs in these lakes. Seasonal and lake effects on BSAFs were detected, while the differences between oligochaetes and other invertebrates were small for PCBs and within a factor of 10 for PAHs. BSAFs for pyrogenic PAHs were much lower than for PCBs, which was explained by stronger sorption to BC and lesser uptake from ingested sediment.     

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.     

Influence of sediment-amendment with single-walled carbon nanotubes and diesel soot on bioaccumulation of hydrophobic organic contaminants by benthic invertebrates

Single-walled carbon nanotubes (SWNT) have extremely high affinity for hydrophobic organic contaminants, considerably higher than natural or refractory (e.g., soot and detrital) carbon found in sediments. To evaluate the effect of sediment-associated SWNT on contaminant uptake from sediments by infaunal deposit feeders, we have conducted a comparative bioaccumulation study using two infaunal estuarine invertebrates. The deposit-feeding meiobenthic copepod Amphiascus tenuiremis and the deposit/suspension-feeding polychaete Streblospio benedicti were exposed to hydrophobic organic contaminants (HOCs) including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and polybrominated diphenyl ethers for 14 days in the presence of sediment amended with (1) SWNTs, (2) NIST diesel soot, or (3) no carbon amendment. Coaddition of SWNT to sediments significantly reduced bioaccumulation of HOCs in S. benedicti; however, soot addition tended to increase the bioaccumulation of these same compounds in the polychaete worm. Bioaccumulation of HOCs from sediments by copepods (A. tenuiremis) was less dependent on black carbon addition to sediment; neither SWNT nor soot significantly impacted bioaccumulation of PAHs from sediment by this organism. Exposure of both copepods and polychaetes to radiolabeled (14C) SWNT in estuarine sediments revealed that these organisms did not assimilate these materials into their tissues, although S. benedicti did ingest 14C-SWNT, as fecal rods from this organism contained identical 14C activity as that of the sediment to which the worms were exposed.     

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.     

Trophic magnification of PCBs and Its relationship to the octanol-water partition coefficient

We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (K(OW)) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (δ1?N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from δ1?N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log K(OW), as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log K(OW)-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of K(OW) on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent K(OW) effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by K(OW)) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical K(OW) and bioaccumulation from field studies are more generalized than previously recognized.     

Temporal bioavailability of organochlorine pesticides and PCBs

Because PCBs and organochlorine pesticides continue to be of global concern, studies that address information gaps, such as factors and influences of spatial and temporal effects on contaminant bioavailability, are valuable. The present study focused on the spatial and temporal distribution of bioavailable organochlorine pesticides and PCBs in surface waters of a contaminated harbor. Passive sampling devices were intensively deployed adjacent to various land uses on the Willamette River, OR, including Portland Harbor and McCormick and Baxter Superfund sites, during summer and fall, extreme conditions, 2001-2004. An increase of bioavailable sigmaDDTs (sum of p,p'-DDT, p,p'-DDD, and p,p'-DDE) concentrations was strongly affected bythe local historic production of DDTs and temporal changes in river conditions. The increase of bioavailable p,p'-DDD and high DDD/DDE ratios observed during summer indicates conditions favoring anaerobic reductive processes. In contrast to sigmaDDTs, the bioavailable concentrations and daily loads of dieldrin and PCBs increased during fall, especially during episodic rainstorms. On the basis of the PCB congener profiles, PCB inputs from urban runoff /sewer overflows were considered likely current sources of bioavailable PCB into the Harbor. The exceedence of the U.S. national and Oregon water quality criteria was a function of the temporal variability of each bioavailable contaminant. This illustrates the impacts associated with temporal changes of bioavailable organochlorine distributions in surface waters and the significance of considering realistic temporal, bioavailability, and site-specific conditions in risk assessment and water quality management.     

Chiral source apportionment of polychlorinated biphenyls to the Hudson River estuary atmosphere and food web

The New York/New Jersey Harbor Estuary is subject to significant contamination of polychlorinated biphenyls (PCBs) from numerous sources, including the historically contaminated Upper Hudson River, stormwater runoff and sewer overflows, and atmospheric deposition from PCBs originating from the surrounding urban area. However, the relative importance of these sources to the estuary's food web is not fully understood. Sources of PCBs to the estuary were apportioned using chiral signatures of PCBs in air, water, total suspended matter, phytoplankton, and sediment. PCBs 91, 95, 136, and 149 were racemic in the atmosphere of the estuary. However, the other phases contained nonracemic PCB 95 and to a lesser extent PCB 149. Thus, the predominant atmospheric source of these congeners is likely unweathered local pollution and not volatilization from the estuary. The similarity in chiral signatures in the other phases is consistent with dynamic contaminant exchange among them. Chiral signatures in the dissolved phase and total suspended matter were correlated with Upper Hudson discharge, suggesting thatthe delivery of nonracemic contaminated sediment from the Upper Hudson, not the atmosphere, controls phytoplankton uptake of some PCBs. Thus, measures to control PCB contamination in the Upper Hudson should be effective in reducing loadings to the estuary's aquatic ecosystem.