Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans, non-ortho polychlorinated biphenyls, and mono-ortho polychlorinated biphenyls in Japanese flounder, with reference to the relationship between body length and concentration

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs), and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) in Japanese flounder (Paralichthys olivaceus, body length 10.4-36.6 cm) collected from Sendai Bay, Japan, were determined using high-resolution gas chromatography-mass spectrometry. The relationship between the concentrations of these compounds (dioxins) and the body length of the Japanese flounder was examined. The total PCDD and total PCDF concentrations did not correlate with body length (both r(2) < 0.1, both p > 0.05), whereas the total non-ortho PCB and total mono-ortho PCB (coplanar polychlorinated biphenyls, Co-PCBs) concentrations were significantly correlated (r(2)= 0.8, p < 0.05 and r(2)= 0.63, p < 0.05, respectively). The bioaccumulation properties of PCDD/Fs in Japanese flounder differed from those of Co-PCBs. Toxicity equivalency quotient (TEQ) values derived from the Co-PCBs made up 46.3%-63.7% of the total TEQ value for all the dioxins. Although the concentrations of non-ortho PCBs were lower than those of mono-ortho PCBs, the TEQ value for non-ortho PCBs was higher than that for mono-ortho PCBs. The TEQ value for non-ortho PCBs increased more with increasing body length than did the values for PCDDs, PCDFs, and mono-ortho PCBs. These results show that from the standpoint of risk management, non-ortho Co-PCBs are the most important of the dioxins in Japanese flounder.     

Sediment influence on congener-specific PCB bioaccumulation by Mytilus edulis: a case study from an intertidal hot spot, Clyde Estuary, UK

An intertidal site in the Clyde Estuary, UK, was selected to evaluate the role of sediment geochemistry on the bioaccumulation of polychlorinated biphenyls (PCBs) by mussels (Mytilus edulis). The area had previously been identified as showing anomalously high levels of PCB contamination (over 1,500 microg kg(-1) total PCB in sediment, 22 congeners). Samples of surface sediment and M. edulis were collected from two closely located sites, one within the anomalous area and another representing typical PCB contamination in the estuary. Sediment samples were separated into grain size fractions and analysed for a range of biomarker compounds, PCBs and sediment mineralogy. The anomalous site showed an atypical association of PCBs with sediment properties, despite both locations showing influence of both petrogenic and pyrogenic organic contamination. Interrogation of data using correlation and principal component analysis showed that sediment mineralogy as well as organic matter composition influenced PCB congener distribution. One sediment source was found to control the PCB concentration in mussels at both locations and clay mineralogy appears to control PCB uptake by biota with preference for higher molecular weight congeners. Overall bioavailability is determined by sediment TOC.     

Remobilization of polychlorinated biphenyls from sediment and its consequences for their transport in river waters

A laboratory experiment was performed to examine the remobilization of indicator polychlorinated biphenyls (iPCBs) from sediments and its results were applied to the real-world data for explaining the transport of PCBs in river. Seven PCB concentrations were determined in three series of model water–sediment systems (3 g of river sediment, three different volumes of distilled water (0.5, 0.25, and 0.15 ml), and 5 mg of biocide) after 11 days of incubation. Solid-phase extraction was used for separation of analytes from the aqueous phase and solvent extraction for isolation of analytes from the sediments, respectively. The extracts were analyzed for individual iPCB congeners using gas chromatography–mass spectrometry method. For each series of the experiment, the concentrations of PCBs in aqueous phase were similar. The average sediment/water partition coefficient value was 10⁴?l/kg. The solubility of individual PCB congeners in water did not influence the desorption of PCBs from the sediment. Although the dominant form of PCBs in a water–sediment system occurs as suspended and colloidal fractions, these compounds are transported mostly in a dissolved form. Suspended and colloidal matter is a major sink for PCBs in low-energy aquatic environments. In contrast, the dissolved PCBs are readily transported in running waters. The mobilization of PCBs from sediments to aqueous phase, with respect to their solubility in water, seems to be limited, thus reducing the risk of secondary pollution.     

PAH and PCB in soils of Switzerland--status and critical review

The surface soil concentrations (0-20 cm) of the Swiss soil monitoring network (NABO) with 105 observation sites representing all major land use types ranged for the sum of 16 EPA PAH (PAH(16)) from 32 to 8465 microg kg(-1) (median 163 microg kg(-1)), for benzo[a]pyrene (BaP) from 0.5 to 1129 microg kg(-1) (median 13 microg kg(-1)) and for the sum of seven IRMM PCB (PCB(7)) from 0.5 to 12 microg kg(-1) (median 1.6 microg kg(-1)). The legal guide values of Switzerland were exceeded for PAH(16) at only three and for BaP at two sites. The PCB(7) concentrations were clearly below any assessment value. The concentration ranges were overlapping between all land use types. Tendencies for higher concentrations were observed at urban and viticulture sites. The overall measurement precision at repeatability conditions ranged from 1 to 37% RSD for PAH(16), BaP and PCB(7). The median bias for the chemical analysis was around zero for PAH(16), +5% for BaP and -5% for PCB(7) with spreads ranging from less than -20% up to more than +30%. The PAH profiles were clearly dominated by phenanthrene. Stratification by land use revealed a prevalence of benzo[a]pyrene at urban and naphthalene at conservation sites. For PCB, the general congener rank order was PCB no. 153 > 138 > 101 > 180. From a broad correlation screening only PAH(16)/BaP (r = 0.88**) were relevant for practical soil protection. The extensive comparison with other studies was severely biased by the lack of harmonisation, especially concerning sampling depth, sampling support, analytical method and the sum calculation procedure.     

Parameters affecting partitioning of 6 PCB congeners in natural sediments

Polychlorinated biphenyls (PCBs) released by bottom sediments were determined by experiments in which the sediments were artificially resuspended using sediment contaminated with PCBs in a particle entrainment simulator (PES). Sediment cores, spikedwith PCBs, were collected from the Housatonic River in Connecticut and run in the PES at simulated shear stresses from 0 to 0.6 N m^-2. Experimental results from these simulations have shown that mean concentration of PCBs in thesolid phase for sites with high volatile organic carbon (VOC) were significantly greater than samples with low VOC; the reversewas true for the water phase. In addition, on a mass load basis,the amount of PCBs found in sediment increased when shear stresses were increased from 0 to 0.6 N m^-2, beyond which shear stress did not affect mass loads in the watercolumn. Partition coefficients (K _p) were determined from PESsediment and water data for the following congeners: PCB 28, PCB 52, PCB 101, PCB 138, PCB 153, PCB 180. K _p was determined to be inversely proportional to total suspended solids (TSS), butdirectly proportional to chlorine content of the congener. Because of the strong influence of TSS and VOC concentrations onK _p values, agitation of samples using a PES better simulatedreal environmental conditions when compared to jar studies where no agitation was employed. Therefore, a device like the PES is more appropriate in obtaining K _p that would be found underreal stream flow conditions when compared to the traditionalway of measuring K _p using the jar study technique.     

Further declines in organochlorines in eggs of red-breasted mergansers from Lake Michigan, 1977–1978 versus 1990 versus 2002

From 1977-1978 to 1990, concentrations of polychlorinated biphenyls (PCBs) and most organochlorine pesticides declined in eggs of red-breasted mergansers (Mergus serrator) nesting on islands in northwestern Lake Michigan. Further declines took place between 1990 and 2002. Between 1977-1978 and 1990 total PCBs decreased 60% (from 21 to 8.5 microg/g, wet weight). An additional decline of 46% took place between 1990 and 2002 (8.5 to 4.6 microg/g). Between 1977-1978 and 1990 p,p (')-DDE decreased 66% (from 6.5 to 2.2 microg/g), and from 1990 to 2002 an additional decline of 36% took place (from 2.2 to 1.4 microg/g). Between 1977-1978 and 1990 dieldrin decreased only 16% (from 0.82 to 0.69 microg/g), but from 1990 to 2002 a 96% decrease occurred (from 0.69 to 0.03 microg/g).     

The New Bedford Harbor Superfund site long-term monitoring program (1993–2009)

New Bedford Harbor (NBH), located in southeastern Massachusetts, was designated as a marine Superfund site in 1983 due to sediment contamination by polychlorinated biphenyls (PCBs). Based on risks to human health and the environment, the first two phases of the site cleanup involved dredging PCB-contaminated sediments from the harbor. Therefore, a long-term monitoring program (LTM) was developed to measure spatial and temporal chemical and biological changes in sediment, water, and biota to assess the effects and effectiveness of the remedial activities. A systematic, probabilistic sampling design was used to select sediment sampling stations. This unbiased design allowed the three segments of the harbor to be compared spatially and temporally to quantify changes resulting from dredging the contaminated sediments. Sediment was collected at each station, and chemical (e.g., PCBs and metals), physical (e.g., grain size), and biological (e.g., benthic community) measurements were conducted on all samples. This paper describes the overall NBH-LTM approach and the results from the five rounds of sample collections. There is a decreasing spatial gradient in sediment PCB concentrations from the northern boundary (upper harbor) to the southern boundary (outer harbor) of the site. Along this same transect, there is an increase in biological condition (e.g., benthic community diversity). Temporally, the contaminant and biological gradients have been maintained since the 1993 baseline collection; however, since the onset of full-scale remediation, PCB concentrations have decreased throughout the site, and one of the benthic community indices has shown significant improvement in the lower and outer harbor areas.     

Screening of dioxin-like compounds in bio-composts and their materials: chemical analysis and fractionation-directed evaluation of AhR ligand activities using an in vitro bioassay

Application of the dioxin responsive-chemical activated luciferase gene expression (DR-CALUX) bioassay to three compost products (kitchen garbage compost, treated sludge compost, and poultry manure compost) and their organic waste materials was performed for the screening of dioxin-like compounds. Phased sample preparation was conducted for the bioassay to yield separate crude, acid-stable, and carbon column fractions. Chemical analyses were also conducted for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs). Their determined WHO-PCDD/PCDF/dl-PCB-TEQ values were compared to the DR-CALUX results expressed as CALUX-TEQ to ascertain their contributions to overall activity. Overall all three compost products were polluted to a low level by persistent PCDD/PCDF/dl-PCBs in a few pg/g WHO-TEQ concentration range. The organic crude fraction showed non-persistent CALUX-TEQ values 2-4 orders of magnitude higher than those of WHO-TEQ. For the acid-resistant fractions of all samples, persistent CALUX-TEQ values were 1-8-fold higher than WHO-PCDD/PCDF/dl-PCB-TEQ values. Both TEQs correlated well for this fraction, which confirms the availability of CALUX for estimation of the actual WHO-TEQ level of the samples using reflux method with 44% sulfuric acid/silica gel, although the compost and material samples examined in this study contained much lower levels of WHO-TEQ: less than 1 pg/g in almost all cases. Additional carbon column treatment enhanced the potency and efficacy of CALUX activity in the three compost samples, which showed 1.6-4.4 times higher values of CALUX-TEQ than those obtained for the acid-resistant fraction. Although further DR-CALUX data collection for compost samples will be necessary, DR-CALUX is useful as a rapid screening method for monitoring dioxin-like compounds in compost.     

Large variation in breast milk levels of organohalogenated compounds is dependent on mother's age, changes in body composition and exposures early in life

We identified factors that are important determinants of body burdens (breast milk levels) of polychlorinated biphenyls (PCBs), dioxins (polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)) and polybrominated diphenyl ethers (PBDEs). PCBs, PCDD/Fs and PBDEs were analysed in breast milk from up to 325 first-time mothers in Uppsala, Sweden, who delivered between 1996 and 2006. Hierarchical clustering was used as a method for identification of groups of compounds with common sources of exposure and similar toxicokinetics. Based on correlations between levels of single compounds/congeners in breast milk, distinctly separated clusters were formed, strongly dependent on structural similarities of the organohalogen molecules. In a multiple regression model, levels of PCBs (except PCB 28), PCDD/Fs and BDE-153 were positively associated with age of the mother and weight loss after delivery and inversely associated with pre-pregnancy BMI (body mass index) and weight gain during pregnancy. Higher levels of mono-ortho PCB TEQ, non-ortho PCB TEQ and BDE-153 in milk were found among women with high physical activity. Women who were breastfed during infancy and grew up on the Baltic coast of Sweden, with high availability of contaminated fish from the Baltic sea, had higher levels of PCBs and PCDD/Fs in breast milk indicating that exposure early in life from breast milk and contaminated fish may still affect body burdens at the time of pregnancy. The importance of current consumption of fatty Baltic fish as a source of exposure was supported by the positive association with breast milk levels of mono-ortho PCB TEQ, PCDF TEQ and BDE-153. The results show that, in contrast to the lower brominated PBDE congeners, the hexa-brominated BDE-153 resembles the chlorinated compounds with regards to determinants in breast milk. This suggests that some of the PBDEs may have toxicokinetic properties and that are similar to the PCBs and PCDD/Fs. Our results show that a few simple advices to women regarding weight changes in connection with pregnancy and consumption of contaminated fatty fish during the whole lifetime may lower the levels of dioxins in breast milk by up to 60%.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Contamination by polychlorinated biphenyls (PCBs) in striped dolphins (Stenella coeruleoalba) from the Southeastern Mediterranean Sea

Concentrations of polychlorinated biphenyls (PCBs) including dioxin-like PCBs (non-ortho, PCB 77, PCB 126, and PCB 169 and mono-ortho, PCB 105, PCB 118, and PCB 156) were measured in different organs and tissues (melon, blubber, liver, kidney, lung, heart, and muscle tissue) of striped dolphins (Stenella coeruleoalba) from the Eastern Mediterranean Sea (Adriatic Sea). The mean highest levels were in blubber and melon, followed by liver, kidney, lung, heart, and muscle tissue. PCB profiles were similar in all tissues and organs being dominated by the higher chlorinated homologues (hexa-CBs, 55.8-62.1%; penta-CBs, 15.4-20.0%; and hepta-CB PCB 180, 12.7-16.5%). Major PCBs in all tissues were congeners 138 and 153 collectively accounting for 50.6-58.3% of the total PCB concentrations, followed by PCB 101, 105, 118, and 180 constituting from 27.0% to 31.0%. PCB levels were higher in adult males than in adult females. The estimated 2,3,7,8-TCDD toxic equivalents of non- and mono-ortho PCBs were much higher than the threshold level above which adverse effects have been observed in other marine mammals species, suggesting that striped dolphins in this region are at risk for toxic effects.     

Immunoassay-based screening of polychlorinated biphenyls (PCB) in sediments: requirements for a new generation of test kits

Polychlorinated biphenyls (PCBs) have been proposed for the inclusion in the European Water Framework Directive (WFD) priority list, currently under revision. Various screening methods have been employed for PCB determination in different environmental matrixes in the last decades, immunoassays being one of the most employed. A literature review reveals that the enzyme-linked immunosorbent assay (ELISA) is the most commonly applied immunoassay for PCB determination in the environment. However, its application to sediments is very limited. A suitability assessment of immunoassay-based analysis for PCB screening in sediments is presented in this work. The significance of available immunoassay-based test kits under the current environmental pollution scenario and their performance against the sensitivity and specificity requirements dictated by the WFD for PCB analysis in sediments is discussed. For example, current detection limits of available test kits for PCB determination in sediments may not be enough for compliance checking under the WFD. In addition, concentration expressed as Aroclor equivalents does not seem to be the way forward. A proposal for adapting available test kits in order to become more suitable tools for PCB screening in sediments is also presented in this study.     

Short-range transport of contaminants released from e-waste recycling site in South China

The transport behaviors of a suite of contaminants released from electronic waste (e-waste) recycling operations, including polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and heavy metals, were evaluated by analyzing the contaminant residues in surface soils sampled in the surrounding area of an e-waste recycling site in South China. Concentrations of PBDEs and PCBs in the soil samples ranged from 0.565 to 2908 ng g(-1) dw and from 0.267 to 1891 ng g(-1) dw, respectively, while soil residues were 0.082-2.56, 3.22-287, and 16.3-162 μg g(-1) dw for Cd, Cu, and Pb, respectively. Concentrations of PBDEs and PCBs in soil decreased with increasing distance from the source of pollution, indicating possible PBDE and PCB contamination in the surrounding areas due to the short-range transport of these compounds from the e-waste recycling site. Although no significant difference in the short-range transport potential among PBDE and PCB congeners was observed, reductions in concentrations of the highly-brominated-BDEs and highly-chlorinated-CBs were slightly quicker than those of their less-halogen-substituted counterparts. Conversely, heavy metals showed the lowest transport potential due to their low vapor pressure, and results showed metals would remain near the pollution source instead of diffusing into the surrounding areas. Finally, mass inventories in areas near the e-waste site were 0.920, 0.134, 0.860, 4.68, 757, and 673 tons for BDE209, PBDEs (excluding BDE209), PCBs, Cd, Cu, and Pb, respectively.     

Analysis of HO-PCBs and PCP in blood plasma from individuals with high PCB exposure living on the Chukotka Peninsula in the Russian Arctic

A trace analytical method is presented for the analysis of hydroxylated polychlorinated biphenyl metabolites (HO-PCBs) and pentachlorophenol (PCP) in human plasma. The described methodology is a modification of a previously validated method used for PCB and organochlorine pesticide analysis. The modified method enables the combined analysis of phenolic and neutral halogenated compounds. A tandem Florisil column is used for separating the HO-PCBs and PCP from the neutral fraction, instead of the more common chemical partitioning. In the same step the neutral fraction is purified for GC analysis. The extraction of the HO-PCBs and PCP was found to be highly dependent on sufficient acidification of the sample and the polarity of the extracting solvent. Analysis of plasma samples gave recovery rates for (13)C(6)-PCP and (13)C(12)-4-HO-CB 187 of 64 and 72%, respectively. The limit of detection ranged between 2-20 pg g(-1) plasma for the HO-PCBs and 5 pg g(-1) plasma for PCP. No matrix interferences were observed in the chromatograms. In plasma samples (n = 15) from the native Chukchi people in Uelen (Russian Arctic), a population with high PCB exposure, the median ratio of sum HO-PCBs to sum PCBs was as high as 0.4 and the sum HO-PCBs and PCBs were significantly correlated (r(2) > 0.7, p < 0.01). The median sum HO-PCBs (10 congeners) was 5920 pg g(-1) plasma with 4-HO-CB 107 as the dominating congener (median: 1670 pg g(-1) plasma). The median PCP level was measured at 642 pg g(-1) plasma.     

Organic pollutants in compost and digestate. Part 1. Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular markers

In Europe, 9.3 x 10(6) t(dry weight (dw)) of compost and digestate are produced per year. Most of this is applied to agricultural land, which can lead to considerable inputs of organic pollutants, such as polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) to soil. This paper presents an inventory of the pollutant situation in source-separated composts, digestates and presswater in Switzerland by a detailed analysis of over 70 samples. PCB concentrations ( summation PCB 28, 52, 101, 118, 138, 153, 180) were significantly higher in urban (median: 30 microg kg(-1)dw, n = 52) than in rural samples (median: 14 microg kg(-1)dw, n = 16). Together with low concentrations in general, this points to aerial deposition on compost input material as the major contamination pathway. Enantiomeric fractions of atropisometric PCB were close to racemic. Median PAH concentration was 3010 microg kg(-1)dw( summation 15PAH, n = 69), and one quarter of the samples exhibited concentrations above the relevant Swiss guide value for compost (4000 microg kg(-1)dw). The levels were influenced by the treatment process (digestate > compost), the season of input material collection (spring-summer > winter > autumn), the particle size (coarse-grained > fine-grained), and maturity (mature > less mature). The main source of PAH in compost was pyrogenic, probably influenced mainly by liquid fossil fuel combustion and some asphalt abrasion, as suggested by multiple linear regression. This study, together with a companion paper reporting on other organic contaminates including emerging compound classes, provides a starting point for a better risk-benefit estimation of the application of compost and digestate to agricultural soil in Switzerland.     

Environmental contaminants in male river otters from Oregon and Washington, USA, 1994–1999

This study reports hepatic concentrations and distribution patterns of select metals, organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 180 male river otters (Lontra canadensis) collected from Oregon and Washington, 1994-1999. Seven regional locations of western Oregon and Washington were delineated based on associations with major population centers, industry or agriculture. Cadmium (Cd) was not found above 0.5 microg g(-1), dry weight (dw) in juveniles, but increased with age in adults though concentrations were generally low (nd-1.18 microg g(-1), dw). Regional geometric means for total mercury (THg) ranged from 3.63 to 8.05 microg g(-1), dw in juveniles and 3.46-12.6 microg g(-1) (dw) in adults. The highest THg concentration was 148 microg g(-1), dw from an apparently healthy adult male from the Olympic Peninsula of Washington. Although THg increased with age in adult otters, the occurrence of the more toxic form methylmercury (MeHg) was not evaluated. Mean OC and PCB concentrations reported in this study declined dramatically from those reported in 1978-1979 from the lower Columbia River. Organochlorine pesticide and metabolite means for both juvenile and adult river otter males were all below 100 microg kg(-1), wet weight (ww), with only DDE, DDD and HCB having individual concentrations exceeding 500 microg kg(-1), ww. Mean SigmaPCB concentrations in both juvenile and adult male otters were below 1 microg g(-1) for all regional locations. Mean juvenile and adult concentrations of non-ortho substituted PCBs, PCDDs and PCDFs were in the low ng kg(-1) for all locations studied.     

Enantiomeric signatures of chiral polychlorinated biphenyl atropisomers in livers of harbour porpoises (Phocoena phocoena) from the southern North Sea

The enantiomeric composition of polychlorinated biphenyl (PCB) atropisomers, including PCB 95, PCB 149 and PCB 132, was measured in 11 livers of harbour porpoises (Phocoena phocoena) from the southern North Sea. Non-racemic enantiomeric ratios (ERs) were found in some samples. The value of ERs in three of the four juvenile porpoises was equal or almost equal to one, while the ERs in all adults differed from racemic and ranged from 1.31 to 2.54 for PCB 95; from 1.19 to 1.81 for PCB 149 and from 0.45 to 0.94 for PCB 132. There were no relationships between the total concentration of PCBs and ERs. To understand the phenomena, the relationships between the ER value of individual chiral congener with age, concentration of total PCBs and PCB congener pattern were discussed. A model of intake and elimination kinetics was set up and it was tested using the ratio between concentration of PCB 153 and PCB 101 in the liver samples. There was a clear trend between the enantiomeric ratios and the ratio between PCB 153 and PCB 101. Considering that PCB 153 is one of the most persistent PCB congeners in marine mammals and PCB 101 is a relatively easy metabolised congener, this trend means that the enantiomeric ratio most likely reflects the proportion of the metabolised congener. The exposure period in contaminated conditions has a strong impact on ERs, and it is suggested that ERs in wildlife, combined with information on their anthropometric data, health status, diet and habitat conditions, might be good indicators of pollution in coastal ecosystems.     

Monitoring of polychlorinated biphenyl contamination and estrogenic activity in water, commercial feed and farmed seafood

We evaluated the concentration and congener distribution of seven "target" polychlorinated biphenyls (PCBs) present in water collected in different aquaculture farms of the Mediterranean area, commercial feeds, and farmed seafood. PCBs were present in feed and in tissues of all the analysed organisms at levels ranging from 1.96 ng g(-1) to 124.00 ng g(-1) wet weight, and in 10.5% of the water samples, at levels from under detection limit to 33.0 ng l(-1) with total PCB concentrations significantly higher in samples from the Tyrrhenian Sea than the Adriatic Sea. PCB congener distribution in tissues resembled that of feed, suggesting that commercial feed is an important source of PCBs. The estrogenicity of organic extracts of the samples was also evaluated by using an in vitro yeast reporter assay. Estrogenic activity higher than 10% of the activity induced by 10 nM 17 beta-estradiol was observed in 20.0% of seafood samples and 15.8% of water samples. Seafood and water samples from the Tyrrhenian Sea were more frequently estrogenic than the Adriatic ones (16.45 versus 4.08%). A significant correlation of total PCB concentrations on biological activity was observed for sea bass and mussels from the Adriatic Sea (p < 0.045 and p < 0.04, respectively), and for sea bass of the Tyrrhenian Sea (p = 0.05). These results indicate the need of an integral approach in the exposure assessment to potential toxic compounds for human via food.     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.