Rainbow trout (Oncorhynchus mykiss) can eliminate chiral organochlorine compounds enantioselectively

Dietary accumulation of four chiral organochlorine compounds--alpha-hexachlorocyclohexane (alpha-HCH), trans-chlordane, and chlorobiphenyls (CBs) 95 and 136-by immature rainbow trout (Oncorhynchus mykiss) was studied to determine if fish can accumulate and eliminate these compounds enantioselectively. Fish rapidly accumulated all four compounds from food spiked at micrograms per gram concentrations during a 40-d feeding period. Depuration half-lives were from 13 d for (+/-)-alpha-HCH to 375 d for (+/-)-CB 136. Fish preferentially eliminated (-)-trans-chlordane and (+)-CB 136, with significant nonracemic residues observed after 20 d. These results are consistent with field measurements of these compounds in fish as well as known metabolic pathways. Enantiomeric fractions (EFs) for these two compounds changed significantly over the course of the experiment, suggesting that trout were enantioselectively biotransforming the compounds during the 238-d depuration phase. CB 95 and alpha-HCH residues were racemic throughout the experiment. High biomagnification factors for CB 95 suggest that it was not metabolized. Minimum values for metabolic elimination rates calculated from EF suggest that at least 58% of the trans-chlordane depuration rate can be attributed to metabolism, and all of the CB 136 depuration rate can be attributed to it. This study highlights the potential of chiral analysis as a tracer of in vivo biotransformation processes of xenobiotic compounds.     

Chiral organochlorine contaminants in blood and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian Arctic

Glaucous gulls (Larus hyperboreus) and their eggs from Svalbard (Norwegian Arctic) have been used as biomonitors of contaminants in the marine environment. In this study, the enantiomer fractions (EFs) of chiral chlordanes and atropisomeric polychlorinated biphenyl (PCB) congeners were determined in the blood plasma of adult male and female glaucous gulls from three breeding colonies in Svalbard. Plasma EFs were similar in magnitude and direction to EFs previously reported in glaucous gulls from other arctic food webs, suggesting overall similarities in the biochemical processes influencing the EFs of bioaccumulated organochlorine (OC) contaminants within the food webs at those locations. Additionally, EFs in yolk of eggs collected concurrently from within the same nesting colonies varied with location, laying date, and OC concentrations, and may be influenced by changes in the local feeding ecology between those colonies. No differences were found between the EFs for any analyte in female gulls compared to those found in egg yolk, indicating that processes involved in the maternal transfer of chlordanes and PCBs to eggs do not modulate the stereochemical ratio between enantiomers. Therefore, the use of eggs as a valuable and noninvasive means of OC biomonitoring may also extend to enantiomer compositions in glaucous gulls, and perhaps also in other seabird species from arctic regions.     

Organochlorine compounds in Lake Superior: chiral polychlorinated biphenyls and biotransformation in the aquatic food web

The enantiomeric composition of seven chiral PCB congeners was measured in the Lake Superior aquatic food web sampled in 1998, to determine the extent of enantioselective biotransformation in aquatic biota. All chiral PCB congeners studied (CBs 91, 95, 136, 149, 174, 176, and 183) biomagnified in the Lake Superior aquatic food web, based on biomagnification and food web magnification factors greater than unity. PCB atropisomers were racemic in phytoplankton and zooplankton, suggesting no biotransformation potential toward PCBs for these low trophic level organisms. However, Diporeia and mysids had significantly nonracemic residues for most chiral congeners studied. This observation suggests that these macrozooplankton can stereoselectively metabolize chiral congeners. Alternatively, macrozooplankton obtained nonracemic residues from feeding on organic-rich suspended particles and sediments, which would imply that stereoselective microbial PCB biotransformation may be occurring in Lake Superior sediments at PCB concentrations far lower than that previously associated with such activity. Widely nonracemic PCB residues in forage fish (lake herring, rainbow smelt, and slimy sculpin) and lake trout suggest a combination of both in vivo biotransformation and uptake of nonracemic residues from prey for these species. Minimum biotransformation rates, calculated from enantiomer mass balances between predators and prey, suggest metabolic half-lives on the order of 8 yr for CB 136 in lake trout and 2.6 yr for CB 95 in sculpins. This result suggests that significant biotransformation may occur for metabolizable PCB congeners over the lifespan of these biota. This study highlights the potential of chiral analysis to study biotransformation processes in food webs.     

Factors affecting phase I stereoselective biotransformation of chiral polychlorinated biphenyls by rat cytochrome P-450 2B1 isozyme

In vitro incubations of rat cytochrome P-450 (CYP) 2B1 isozyme with three chiral polychlorinated biphenyl (PCB) congeners (PCBs 45, 95, and 132) were performed to investigate factors affecting phase I stereoselective biotransformation. Rat CYP2B1 preferentially biotransformed the second-eluting atropisomers of PCBs 45 and 95 at low substrate concentration ranges (≤15 μM). Biotransformation competition by different congeners was also observed, with increasing competition at higher chlorination. Competition decreased the biotransformation rates of each congener stereoselectively, affecting atropisomeric composition. No atropisomeric enrichment was observed for PCB 132 upon incubation of the racemate. However, under the same conditions, significant differences in biotransformation kinetics were observed in individual atropisomer incubations, indicating that (+)-PCB 132 and (-)-PCB 132 were competitively biotransformed. Homology modeling and docking studies suggested that each atropisomer had different interactions with rat CYP2B1 and could dock with the isozyme at different locations. This is one possible explanation for stereoselective biotransformation and competition of chiral PCBs at the molecular level. Our results suggest that the lack of predictive capability for stereoselectivity of PCBs and other chiral pollutants in biota may be due to competitive and/or inhibitory activities of different substrates, including individual enantiomers of the same compound.     

Enantioselective degradation of organochlorine pesticides in background soils: variability in field and laboratory studies

Variability in the enantioselective degradation of chiral organochlorine pesticides (alpha-HCH, cis- and trans-chlordane (CC and TC), and o,p'-DDT) in the field and laboratory was investigated. Background soils presumably receive the same EF signature of a compound via atmospheric deposition and then degrade that compound in a way that can vary over small spatial areas. Background soils from woodland and grassland areas were sampled to compare chiral signatures and determine the spatial variability within a few square meters. The enantiomer fractions, EF = areas of the (+)/[(+)+(-)]-enantiomers, showed variability between and within ecosystems. For example, the EF of CC varied between 0.272 -and 0.558 in nine samples taken over a few square meters, and a range of 0.431-0.506 was found within depths of a few centimeters. Woodland and grassland soils were spiked with alpha-HCH, TC, CC, and o,p'-DDT, and one portion was placed in the field to monitor changes in EF under in situ conditions and the other taken to the laboratory. In general, the enantiomer degradation preferences in the laboratory paralleled those in the field, with some differences. Soil organic matter content and pH exerted a minor influence on this variability. The results of this study have implications for the use of chiral compounds to make inferences about air-soil exchange and for the mechanisms of biodegradation/ biotransformation of anthropogenic compounds in soils.     

Bioaccumulation, biotransformation, and metabolite formation of fipronil and chiral legacy pesticides in rainbow trout

To assess the fate of current-use pesticides, it is important to understand their bioaccumulation and biotransformation by aquatic biota. We examined the dietary accumulation and enantioselective biotransformation of the chiral current-use pesticide fipronil, along with a mixture of selected chiral [alpha-hexachlorocyclohexane (alpha-HCH), heptachlor epoxide (HEPX), polychlorinated biphenyls (PCBs) 84, 132, 174, o,p'-DDT, and o,p'-DDD] and nonchiral (p,p'-DDT, p,p'-DDD) organochlorine compounds in juvenile rainbow trout (Oncorhynchus mykiss). Fish rapidly accumulated all compounds, as measured in the carcass (whole body minus liver and GI tract) during the 32 d uptake phase, which was followed by varying elimination rates of the chemicals (half-lives (t1/2s) ranging from 0.6 d for fipronil to 77.0 d for PCB 174) during the 96 d depuration period. No biotransformation was observed for alpha-HCH, HEPX, PCB 174, o,p'-DDT, or o,p'-DDD based on consistent enantiomeric fractions (EFs) in the fish and their t1/2s falling on a log K(ow)--log t1/2 relationship established for recalcitrant contaminants in fish. p,p'-DDT and PCBs 84 and 132 were biotransformed based on the former's t1/2 position below the log K(ow)--log t1/2 relationship, and the PCBs change in EF. Fipronil was rapidly biotransformed, based on a change in EF, a t1/2 that fell below the log K(ow)--log t1//2 relationship, which accounted for 88% of its elimination, and the rapid formation of fipronil sulfone, a known metabolite. Fipronil sulfone was found to persist longer (t1/2 approximately 2 d) than its parent compound fipronil (t1/2 approximately 0.6 d) and needs to be considered in fate studies of fipronil. This research demonstrates the utilities of the log K(ow)--log t1/2 relationship as a mechanistic tool for quantifying biotransformation and of chiral analysis to measure biotransformation in fish.     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

Sediment characteristics affecting desorption kinetics of select PAH and PCB congeners for seven laboratory spiked sediments

Measures of desorption are currently considered important as potential surrogates for bioaccumulation as measures of the bioavailability of sediment-sorbed contaminants. This study determined desorption rates of four laboratory spiked compounds, benzo[a]pyrene (BaP), 2,4,5,2',4',5'-hexachlorobiphenyl (HCBP), 3,4,3',4'-tetrachlorobiphenyl (TCBP), and pyrene (PY), to evaluate the effect of sediment characteristics. The compounds were sorbed onto seven sediments with a broad range of characteristics. Desorption was measured by Tenax-TA extraction from aqueous sediment suspensions. Desorption rates were modeled using an empirical three compartment model describing operationally defined rapid, slow, and very slow compartments. The sediments were characterized for plant pigments, organic carbon (OC), total nitrogen (TN), lipids, NaOH extractable residue, lignin, amino acids, soot carbon, and particle size fractions. Desorption from the rapid compartment for each of the planar compounds BaP, PY, and TCBP was significantly correlated to sediment characteristics that could be considered to represent younger (i.e., less diagenetically altered) organic matter, e.g., plant pigment, lipid, and lignin contents. However, for these compounds there were no significant correlations between desorption and OC, TN, soot carbon, or amino acid contents. HCBP desorption was different from the three planar molecules. For HCBP, the flux from the rapid compartment was negatively correlated (0.1 > p > 0.05) with the OC content of the sediment. Overall, HCBP desorption was dominated by the amount of OC and the particle size distribution of the sediments, while desorption of the planar compounds was dominated more by the compositional aspects of the organic matter.     

Organochlorine pesticide residues in archived UK soil

Archived background soils ("Broadbalk', 1944-1986) and sludge-amended soils ("Luddington", 1968-1990), collected from long-term agricultural experiments in the UK, were analyzed for a range of organochlorine (OC) pesticides to establish trends over time. Concentrations typically ranged from 0.1 to 10 ng/g of soil (dry weight), with gamma-hexachlorocyclohexane (gamma-HCH), dieldrin, and p,p'-DDE consistently having the highest concentrations. The trends in the Broadbalk background soils are largely consistent with usage patterns, with peak concentrations occurring in the 1960s for DDTs and between the 1960s and the 1980s for the other OCs. In the Luddington control and sludge-amended soils, several of the OCs show a significant decline in concentrations from the late 1960s to 1990, with half-lives ranging from approximately 7 years (alpha-HCH) to approximately 25 years (dieldrin). The sludge-amended plot received 125 tonnes of sludge per ha in 1968, which was mixed in to a depth of 15 cm. It appears that the sludge treatment had little effect on concentrations in the soil, with no significant difference between control soil and sludge-amended soil for most compounds, except for HCB, p,p'-DDE, and dieldrin. Enantiomeric fractions (EFs) of some chiral pesticides (alpha-HCH, cis- and trans-chlordane, and o,p'-DDT) were determined in the Luddington soils. Results reveal that enantioselective degradation of OC pesticides is occurring in these soils for trans-chlordane (TC) and cis-chlordane (CC). However, the depletion over time is not statistically significant, and there is no statistically significant difference between EFs in the control soil and sludge-amended soil. This indicates that enantioselective microbial degradation was not consistent over time and that the addition of sludge to soil did not significantly alter the enantiomeric preference of the microbial community.     

Emission of chiral organochlorine pesticides from agricultural soils in the cornbelt region of the U.S

Several organochlorine pesticides are chiral molecules manufactured as racemic mixtures. Past research has shown that selective degradation of pesticide enantiomers by microorganisms occurs resulting in nonracemic signatures in soils. In this work, volatilization of chiral pesticides from soil was investigated to determine if enantioselective breakdown in soils could be used as a source signature to track releases of chiral pesticides to the atmosphere. Air samples were taken directly above agricultural soils at several sites, and enantiomeric signatures were found to be nonracemic following patterns found in the soil. A follow up study at one site showed that for most compounds concentration decreased with increasing height above the soil, while enantiomer fractions for chiral pesticides were similar to that found in the soil, signifying the soil as a source to the air. The enantiomer fractions of ambient air samples from rural nonagricultural areas in the region were also found to be nonracemic.     

Organochlorine compounds in trout from lakes over a 1600 meter elevation gradient in the Canadian Rocky Mountains

The effect of altitude on the concentration and composition of organochlorine compounds (OC) in troutwas investigated along an elevation gradient of 1600 m in the Canadian Rocky Mountains. The eight lakes sampled were within or adjacent to national parks in sparsely settled parts of Alberta and British Columbia, thus contaminants were assumed to have derived from long-range atmospheric transport. Concentrations of several OCs in trout increased significantly with lake elevation. In general, these increases were most pronounced for the higher K(ow) pesticides (i.e., dieldrin and DDTs), and less pronounced for lower K(ow) pesticides (e.g., HCHs and HCB) and PCBs. Most OC concentrations in trout were inversely correlated with fish growth rate. Growth rate explained more of the variation for some OCs (particularly PCBs) than lake elevation. Differences in trophic position (indicated by delta15N) explained little of the variation in OC concentration in comparison to other factors such as lake elevation and the growth rate and age of trout. Using principal component analysis (PCA), we identified the importance of lake elevation and octanol/water partition coefficient (K(ow)) to the OC composition of trout.     

Changes in concentrations of perfluorinated compounds, polybrominated diphenyl ethers, and polychlorinated biphenyls in Norwegian breast-milk during twelve months of lactation

At present, scientific knowledge on depuration rates of persistent organic pollutants (POPs) is limited and the previous assumptions of considerable reduction of body burdens through breast-feeding have recently been challenged. We therefore studied elimination rates of important POPs in nine Norwegian primiparous mothers and one mother breast-feeding her second child by collecting breast-milk samples (n = 70) monthly from about two weeks to up to twelve months after birth. Perfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and polychlorinated biphenyls (PCBs) were determined in the breast-milk samples. Linear mixed effect models were established for selected compounds, and significant decreases in the range of 1.2-4.7% in breast-milk concentrations per month were observed for a wide range of PCBs and PBDEs. For the first time, depuration rates for perfluorooctylsulfonate (PFOS) and perfluorooctanoic acid (PFOA) are presented, being 3.8 and 7.8% per month, respectively (p < 0.05). The relative amount of the branched PFOS isomers in the breast-milk samples was 18% on average (range 6-36%, RSD 30%). There were no significant differences in isomer pattern between the mothers, or changes during the lactation period. After a year of nursing the breast-milk concentrations of PFCs, PBDEs, and PCBs were reduced by 15-94%.     

Organochlorine pesticide and polychlorinated biphenyl concentrations in snow, snowmelt, and runoff at Bow Lake, Alberta

We present analyses of the concentrations of organochlorine (OC) contaminants (including organochlorine pesticides and PCBs) in snow, snowmelt, and runoff in glacier and snowmelt fed streams at Bow Lake, Alberta in two contrasting hydrological years (1997 and 1998). The study investigates the variability in OC burdens in snow across the catchment, the elution of OCs from the snowpack, and the relationship between OC concentrations in streams and the annual snowpack. Snowpacks in forested sites were thinner and had lower OC concentrations than snowpacks in open or sparsely vegetated sites. The first snowmelt samples exhibited very high contaminant concentrations relative to the snowpack, and even the more hydrophobic compounds (Dieldrin, DDTs, and PCBs) were highly concentrated in meltwater. Interannual changes in the mean OC concentrations in streams did not reflect year-to-year changes in the snowpack contaminant concentrations. The results indicate that the extent of glacial ice melt may be more important than mean snowpack burdens as a control on OC concentrations in runoff in glacial catchments.     

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic bed sediment

Enantiomeric ratios (ERs) for eight polychlorinated biphenyl (PCB) atropisomers were measured in aquatic sediment from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic ERs for PCBs 91, 95, 132, 136, 149, 174, and 176 were found in sediment cores from Lake Hartwell, SC, which confirmed previous inconclusive reports of reductive dechlorination of PCBs at these sites on the basis of achiral measurements. Nonracemic ERs for many of the atropisomers were also found in bed-sediment samples from the Hudson and Housatonic Rivers, thus indicating that some of the PCB biotransformation processes identified at these sites are enantioselective. Patterns in ERs among congeners were consistent with known reductive dechlorination patterns at both river sediment basins. The enantioselectivity of PCB 91 is reversed between the Hudson and Housatonic River sites, which implies that the two sites have different PCB biotransformation processes with different enantiomer preferences.     

Enantioselective biotransformation of chiral PCBs in whole poplar plants

Chiral PCBs have been used as molecular probes of biological metabolic processes due to their special physical, chemical, and biological properties. Many animal studies showed the enantioselective biotransformation of chiral PCBs, but it is unclear whether plants can enantioselectively biotransform chiral PCBs. In order to explore the enantioselectivity of chiral PCBs in whole plants, poplars (Populus deltoides × nigra, DN34), a model plant with complete genomic sequence, were hydroponically exposed to 2,2',3,5',6-pentachlorobiphenyl (PCB95) and 2,2',3,3',6,6'-hexachlorobiphenyl (PCB136) for 20 days. PCB95 and PCB136 were shown to be absorbed, taken-up and translocated in whole poplars, and they were detected in various tissues of whole poplars. However, the enantioselectivity of poplar for PCB95 and PCB136 proved to be quite different. The first eluting enantiomer of PCB95 was enantioselectively removed in whole poplar, especially in the middle and bottom xylem. It was likely enantioselectively metabolized inside poplar tissues, in contrast to racemic mixtures of PCB95 remaining in hydroponic solutions in contact with plant roots of whole and dead poplars. Unlike PCB95, PCB136 remained nearly racemic in most parts of whole poplars after 20 days exposure. These results suggest that PCB136 is more difficult to be enantioslectively biotransformed than PCB95 in whole poplars. This is the first evidence of enantioselectivity of chiral PCBs in whole plants, and suggests that poplars can enantioselectively biotransform at least one chiral PCB.     

Residues of persistent organochlorine contaminants in southern elephant seals (Mirounga leonina) from Elephant Island, Antarctica

Contamination of blubber tissues by organochlorine pesticides (OC) and PCBs was assessed in female and male pups and juveniles, as well as in adult females and subdominant adult males of the Southern elephant seal, Mirounga leonina, from Elephant Island in the Antarctic Peninsula. All residues of persistent organochlorine contaminants analyzed were found in blubber samples, except for beta-HCH, endosulfan II, endrin, heptachlor, and aldrin. The relative concentrations of the analytes detected were sigmaDDT > sigmaPCB > sigmachlordane > mirex > dieldrin > HCB> sigmaendosulfan > methoxychlor > sigmaHCHs > other OC pesticides. OC and PCBs concentrations were 1 or 2 orders of magnitude lower than those found in pinnipeds from northern hemisphere. The ratio sigmaDDT/sigmaPCB was higher in southern elephant seals. The relative importance of some OC residues indicates that pesticides used either currently or in the recent past in countries in the southern hemisphere are the sources of contamination in the Antarctic region. Data showed that concentrations of contaminants generally increased from pups < juveniles < adults and suggested that pups accumulated contaminants through transfer from the mother seals via transplacental and lactational routes.     

Chiral PCB signatures in air and soil: implications for atmospheric source apportionment

Enantiomeric fractions (EFs) of chiral PCBs 95, 136, and 149 were measured in samples of topsoil and outdoor air at one urban and one rural location in the U.K. West Midlands between early 2001 and early 2002. While EFs in air were essentially racemic, those in topsoil indicated appreciable enantioenrichment of the second eluting enantiomer for PCB 95 and the (+) enantiomer for PCBs 136 and 149. This suggests (i) that essentially all atmospheric PCBs at both sites arise from racemic (i.e, primary) sources, rather than volatilization from soil and (ii) that appreciable enantioselective degradation of the monitored PCBs in topsoil occurs. This is one of only two reports of enantioselective degradation of PCBs in soil worldwide and is particularly noteworthy as it is occurring at PCB concentrations (e.g., 5.9 pg g(-1) for PCB 136) that are typical of the U.K. and other industrialized countries. The extent of enantioselective degradation in this study for PCBs 95 and 136 is consistent with those reported for soils in the Greater Toronto area (GTA). In contrast, enantioselective degradation of PCB 149 observed in this study is--while consistent with that reported for U.K. lacustrine sediments--in excess of that observed in either the GTA soil study or in U.S. lake sediments.     

Exchange of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) between air and a mixed pasture sward

To improve understanding of air-to-vegetation transfer of persistent organic pollutants (POPs), uptake and depuration of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) between grass sward and air was investigated. Pasture swards were placed in fanned (2 m s(-1) wind speed) and unfanned conditions for a period of 20 days and sampled at intervals. Depuration was carried out after a short (4 days) and a long (14 days) exposure period. Prior to contamination, a mixed pasture sward at a semi-rural location contained sigmaPCN concentrations 15-20% of the sigmaPCB concentration. Uptake of both PCBs and PCNs was broadly linear in fanned and unfanned conditions over the 20-day period, i.e., the pasture did not reach equilibrium with the air. Uptake rates (fluxes) were greater under the fanned conditions. The difference in uptake rates between fanned and unfanned conditions increased with degree of chlorination for both PCBs and PCNs, ranging between a factor of 2 for tri-chlorinated PCBs and PCNs and a factor 5 for octa-chlorinated PCBs. Depuration results over the first hours were very scattered, showing an initial period of loss, followed by an increase in concentrations, possibly as a result of re-volatilization of PCBs from the soil in the trays, with consequent recapture by the overlying sward. Rapid clearance was observed over the following days, but depuration of PCBs and PCNs was still incomplete after 14 days, with 20% of the initial concentration of the sigmaPCBs and 10% of the sigmaPCNs retained by the sward. There was no difference in the proportion of POPs retained in the sward between the 4- and 14-day contamination treatments. POP-specific differences in the amount of compound "trapped" in leaves after contamination were observed. The results show that, although changes in the rate of air movement around a pasture have an effect on the uptake rate of POPs into the vegetation, plant-side resistance controls both the air-to-pasture and pasture-to-air exchange of gas-phase PCBs and PCNs; i.e., differences between plant species in cuticle composition and/or structure affecting the permeability of the cuticle are of greater importance than differences in leaf morphology affecting aerodynamic roughness.     

Investigation into the importance of the stomatal pathway in the exchange of PCBs between air and plants

The transfer of persistent organic pollutants (POPs) from air to vegetation is an important air-surface exchange process that affects global cycling and can result in human and wildlife exposure via the terrestrial food chain. To improve understanding of this process, the role of stomata in uptake of gas-phase polychlorinated biphenyls (PCBs) was investigated using Hemerocallis x hybrida "Black Eyed Stella", a plant with a high stomatal density. Uptake of PCBs was monitored over a 72-h period in the presence and absence of light. Uptake rates were significantly greater in illuminated (stomata open) plants than unilluminated (stomata closed) plants for 18 of the 28 measured PCB congeners (p < 0.05). Depuration of PCBs was monitored in a subsequent experiment over a period of 3 weeks. Levels after 3 weeks of depuration time were still much higher than the concentration prior to contamination. Tri- and tetrachlorinated PCBs showed the greatest depuration, with less than 20% and 50% of accumulated PCBs respectively remaining, while approximately 70% of higher chlorinated PCB congeners remained in the plants at the end of the experiment. Treatments with/without light (to control stomatal opening during uptake) and with/without abscisic acid (ABA) application (to control stomatal opening during depuration) were compared. After contamination indoors for 3 days, there was a significantly higher concentration of PCBs (p < 0.05) in the light contaminated plants than the dark-contaminated plants for 13 of the 28 measured PCB congeners. The ABA treatment affected depuration of PCB-18 only. "Light/ABA-treated" plants had a significantly slower depuration rate for PCB-18 than "light/untreated", "dark/ABA-treated", and "dark/untreated" plants (p < 0.05). The results of the study indicate that there is a stomatal effect on the rate of exchange of PCBs between Hemerocallis leaves and air.     

Addition of activated carbon to sediments to reduce PCB bioaccumulation by a polychaete (Neanthes arenaceodentata) and an amphipod (Leptocheirus plumulosus)

This work examines the effects of adding coke or activated carbon on the bioavailability of polychlorinated biphenyls (PCBs) in contaminated sedimentfrom South Basin at Hunters Point, San Francisco Bay. We show with 28-day sediment exposure tests that PCB bioaccumulation in a polychaete (Neanthes arenaceodentata) is reduced by 82% following 1-month contact of sediment with activated carbon and by 87% following 6-months contact of sediment with activated carbon. PCB bioaccumulation in an amphipod (Leptocheirus plumulosus) is reduced by 70% following 1-month contact of sediment with activated carbon and by 75% after 6-months contact of sediment with activated carbon. Adding coke had a negligible effect on reducing PCB bioaccumulation, probably because of the low specific surface area and the slow kinetics of PCB diffusion intothe solid coke particles. Reductions in congener bioaccumulation with activated carbon were inversely related to congener Kow, suggesting that the efficacy of activated carbon is controlled by the mass-transfer rate of PCBs from sediment and into activated carbon. We find that reductions in aqueous PCB concentrations in equilibrium with the sediment were similar to reductions in PCB bioaccumulation. While no lethality was observed following activated carbon addition, growth rates were reduced by activated carbon for the polychaete, but not for the amphipod, suggesting the need for further study of the potential impacts of activated carbon on exposed communities. The study suggests that treatment of the biologically active layer of contaminated sediments with activated carbon may be a promising in-situ technique for reducing the bioavailability of sediment-associated PCBs and other hydrophobic organic compounds.