Selective supercritical fluid extraction as a tool for determining the PCB fraction accessible for uptake by chironomid larve in a limnic sediment

Selective supercritical fluid extraction (SFE) at 40 degrees C, 400 bar and 60 min was used to selectively remove bioavailable PCBs from a naturally contaminated limnic sediment. The extraction decreased the sediment concentrations of the nine studied PCBs by 54% (on average). Chironomid larvae were thereafter cultured in pre-extracted sediment as well as in untreated sediment to study the differences in uptake of PCBs in the two cultures. While the prevailing equilibrium partitioning (EqP) theory predicts a 54% decrease in PCB uptake by the chironomids in the pre-extracted sediment, with a maintained biota-to-sediment accumulation factor (BSAF), a decrease in PCB uptake by 91% was observed. For all investigated PCBs the BSAFs were on average 81% lower in the cultures with pre-extracted sediment than in the untreated systems. The data allowed for a calculation of the bioavailable fraction, which was estimated to 60%. This is very close to the 54% removed by selective SFE, demonstrating the possibility of using SFE as a tool to determine the bioavailable PCB fraction in a polluted sediment.     

Selective supercritical fluid extraction to estimate the fraction of PCB that is bioavailable to a benthic organism in a naturally contaminated sediment

Selective supercritical fluid extraction (SFE) at 40 degrees C, 120 bar and 60 min was utilised as a means to estimate the bioavailable fraction of PCBs to chironomid larvae in a naturally contaminated limnic sediment. This extraction methodology removed about 50% of the PCBs from the sediment. According to the equilibrium partitioning theory, organisms in that sediment should decrease their uptake from the sediment to the same extent, biota-to-sediment accumulation factors (BSAFs) thus remaining constant. Surprisingly, the BSAFs for 11 PCB congeners decreased some 40% for the selectively extracted sediment as compared to BSAFs for organisms dwelling in untreated sediment. The results were statistically significant at the 0.001 level using a paired t-test. This can only be interpreted so that selective SFE removed easily available PCBs preferentially, leaving more tightly bound PCBs behind. Hence, by fine-tuning extraction conditions, this methodology might be used to estimate bioavailable fractions by chemical means.     

Comparison of supercritical fluid extraction and Soxhlet extraction for the determination of PCBs in seaweed samples

The efficiency of supercritical fluid extraction for the determination of 12 polychlorinated biphenyls from algae samples is compared to Soxhlet extraction. Analytical detection limits for the individual congeners ranged from 0.62 microgl(-1) to 19 microgl(-1). Recovery was tested for both methods using standard addition procedure. At maximum spike level of concentration, the mean recoveries were not significantly different (P>0.05) of all PCBs studied, with the exception of PCBs 28, 52, 77 and 169. Method precision for Soxhlet extraction (< or =3.9%) was slightly better than for SFE (< or =9.2%). Although both methods yield comparable results, SFE offers the advantage of detecting all PCBs studied at lower concentrations, reducing extraction time, and reducing the amount of solvents needed. The optimized methods were applied to the analysis of three real seaweed samples, except for PCB101 the concentrations of all PCBs were low or below the detection limits. The levels of PCB101 found in sample 1 were 6.6+/-0.54 ng g(-1) d.w., in sample 2 the levels were 8.2+/-0.86 ng g(-1) d.w. and in sample 3 they were 7.7+/-0.08 ng g(-1) d.w.     

Measuring bioavailability of polychlorinated biphenyls in soil to earthworms using selective supercritical fluid extraction

If the release mechanisms during selective chemical extraction of persistent organic pollutants (POP) mimic release mechanisms in natural systems during biological uptake, then a selective non-exhaustive extraction could give a quantitative measure of the bioavailable POP fraction. Supercritical fluid extraction (SFE) is suggested as a possible technique to estimate the amount of bioavailable polychlorinated biphenyls (PCBs) at contaminated sites and hence serve as a new tool in risk assessment. The uptake of PCBs by earthworm (Eisenia foetida) was investigated. PCB contaminated soil was pre-extracted with selective non-exhaustive SFE (50 degrees C, 350 bar, 1h), which removed on average 70% of the individual PCBs. Earthworms were placed in this pre-extracted soil, as well as in untreated soil. After 10 days, the PCB uptake by earthworms in the two systems was compared. The bioaccumulation factor (BAF) was 83% lower in the pre-extracted system than in the untreated system, demonstrating that SFE extracts primarily bioavailable contaminants. From the data, the bioavailable fraction could also be calculated to be 75%, which is very close to the 70% removed by SFE under the applied conditions. This suggests that the chemical methodology is capable of measuring the bioavailable fraction very accurately in this system.     

Study of the distribution of the polychlorinated biphenyls in the milk fat globule by supercritical fluid extraction

The distribution of polychlorinated biphenyls (PCBs) in the milk fat globule has been studied by sequential extraction of four different lipidic fractions from powdered full-fat milk with supercritical carbon dioxide. Extractions were carried out in the dynamic mode in the pressure range 13.6-23.3 MPa at a temperature of 50 degrees C. The levels of PCBs and short-chain triglycerides (SCT), medium-chain triglycerides (MCT) and long-chain triglycerides (LCT), as well as the cholesterol in these four supercritical fluid extraction (SFE) fractions were determined. Extracts obtained at lower pressures were found to be enriched in PCBs, SCT, MCT and cholesterol, while the concentrations of all these analytes decreased for subsequent extractions. Satisfactory quadratic correlations were found between the PCB and SCT and MCT levels (r2 in the range 0.9-0.999), and between the PCB and cholesterol levels (r2 in the range 0.8-0.999, except for PCB 105) determined in the SFE fractions. These results suggested a similar distribution of the PCBs and the cholesterol in the milk fat globule. This conclusion was also supported by the comparison of the PCBs and the cholesterol chemical structures as well as by the total PCB levels determined by SFE to those obtained by using different extraction methods. The classical requirement for the analysis of this kind of lipophilic pollutants of an exhaustive extraction of the lipids of the matrix to ensure their quantitative recovery has been revised.     

Selective supercritical fluid extraction to identify aged sediment-bound PCBs available for uptake by eel

A naturally contaminated sediment was partially extracted with selective supercritical fluid extraction (SFE) to remove a fraction of supposedly bioavailable PCBs from the matrix. Eels (Anguilla anguilla) were cultured in systems with untreated and pre-extracted sediment, respectively, and it was shown that the SFE treatment selectively removed bioavailable PCBs from the sediment, since relative biota-to-sediment accumulation factors (BSAFs) for the eight studied PCB congeners were much lower in the pre-extracted than in the untreated system at the end of the study. Relative BSAF values decreased with about the same relative amount for all eight congeners, independent of the degree of chlorination and the initial concentration in the sediment. The results demonstrate the ability of SFE to selectively remove sediment-bound PCBs that are available for uptake by the eels, thus demonstrating the feasibility of using selective SFE to estimate bioavailability of PCBs in sediments.     

Improved extraction procedures for polychlorinated biphenyls in solid samples with aqueous sodium hydroxide under autoclave conditions

The efficacy of the extraction of polychlorinated biphenyls (PCBs) from varnish-infiltrated insulating papers as a model of solid materials with an aqueous sodium hydroxide (NaOH) by autoclaving at 121 degrees C for 30 min was compared with those for the conventional procedures, i.e., saponification with 1 N ethanolic NaOH in a boiling water bath for 60 min and extraction with benzene in a Soxhlet apparatus. The newly invented autoclaving method was found to be superior to the conventional ones, yielding approximately 5- to 6-fold cumulative PCB congeners without being accompanied by extended decomposition. Therefore, the autoclave-based sample treatment is recommended for more accurate determination of PCBs in the case of PCB-impregnated solid materials such as hardened oils and resin-coated or -infiltrated papers instead of being treated conventionally.     

Seasonal variation of the distribution of PCBs in sediments and biota in a PCB-contaminated estuary

To elucidate the effects of seasonal variation of precipitation on the distribution of polychlorinated biphenyls (PCBs) in estuarine sediments and benthic feeders, PCB concentrations of river surface sediments and mullet fish (Liza macrolepis) were investigated in the estuary of Er-Jen River near former PCB contamination sites before and after each wet season from 2002 to 2004. Analyses of grain size distribution and organic matter revealed that the pre-existing surface sediments were covered by and mixed with the soil particulates brought by surface runoff after each wet season. Obvious increment of PCB content and significantly elevated fraction (p < 0.005) of light PCBs of the river mouth’s sediments after each wet season indicated that the invading particles were rich in unweathered PCBs. PCBs previously buried in the surface soil of heavily contaminated sites were flushed into this estuary through surface runoff. The precipitation altered the PCB patterns in sediment organic matter, the dietary source of mullet, and consequently changed that of mullets accordingly, which all possessed significant greater fraction of light PCBs. In this study, it was demonstrated that seasonal summer precipitation affected the distribution of PCBs on surface sediments and the mullets of this estuary. PCB residuals retained in this region still pose potential threats to biota resided here.     

The relation between levels of selected PCB congeners in human serum and follicular fluid

Individual congener and total PCB concentrations were determined in serum and follicular fluid obtained from women undergoing assisted reproductive technologies (in-vitro fertilization and embryo replacement). Although the mean individual PCB levels revealed varying degrees of contamination, the results fall in the same range as that observed by other investigators. Except for PCB 118, correlations between levels in serum and follicular fluid were strong, and statistically significant at p < 0.05. Moreover PCB 153, a major and very stable PCB congener has been shown to correlate to the total amount of PCBs (r = 0.994, and r = 0.987, for serum and follicular fluid, respectively). The same accumulation patterns of PCBs for serum and follicular fluid have been observed.     

Polychlorinated biphenyls in surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in East China Sea

The spatial distribution and source of polychlorinated biphenyls (PCBs) in 30 surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in Eastern China were analysed. Total concentrations of PCBs ranged from 9.33 to 19.60 ng g⁻¹ dry weight for all the sampling stations. The observed PCB levels were lower than those in areas of high urbanisation or contamination in the bay. Low-chlorinated PCBs, dominated by tri-PCB, were identified as the prevalent contaminate of surface sediments, and the top three PCB congeners were lighter chlorinated congeners (PCB 8, PCB 18 and PCB 28). These results were in agreement with the fact that tri-PCB compounds are the dominant contaminants in China. The result of the principal component analysis revealed that all samples were similar in composition to Aroclor 1242, suggesting they might originate from electrical capacitors and transformers. The levels of PCBs were significantly correlated with the total organic carbon in the sediments.     

Occurrence and possible sources of polychlorinated biphenyls in surface sediments from the Wuhan reach of the Yangtze River, China

Twenty-seven surface sediment samples were collected from the mainstream and eight tributaries of the Wuhan reach of the Yangtze River, China, in 2005, in order to assess the distribution, possible sources, and potential risk of polychlorinated biphenyls (PCBs) in the environment. The total concentrations of PCBs (the sum of 39 congeners) ranged from 1.2 to 45.1 ng g⁻¹ dry weight, with a mean value of 9.2 ng g⁻¹. Sediment samples with the highest PCB concentrations came from the tributary sites, which are closer to PCB sources. Conversely, PCB concentrations in the sediment from the mainstream sites of Yangtze River were relatively low. The observed PCB levels were higher than those found in the sediments of other rivers in China, but lower than those in river sediments from other urban areas and harbors around the world. Low-chlorinated PCBs, dominated by tetra-PCBs and penta-PCBs, were identified as being prevalent in the surface sediments. Correlation analyses between the PCBs and the geochemistry and heavy metal content of the sediments suggest that the washing of these compounds from the land into the river by floods and heavy rains, or industrial wastewater and domestic sewage, may be the major sources of the PCBs. According to established sediment quality guidelines, the risk of adverse biological effects from the levels of PCBs recorded at most of the studied sites should be insignificant, although the higher concentrations at other sites could cause acute biological damage.     

Multicriteria optimisation of a simultaneous supercritical fluid extraction and clean-up procedure for the determination of persistent organohalogenated pollutants in aquaculture samples

A useful tool based on a single-step extraction and clean-up procedure for the determination of 15 organohalogenated pollutants (including brominated flame retardants) in aquaculture samples, using aluminium oxide basic and acidic silica gel in the supercritical extraction cell followed by gas chromatography with electron capture detection or mass spectrometry has been developed. This effective clean-up step ensures a minimum of chromatographic difficulties related to complex matrix components such as aquaculture feed. The extraction procedure has been screened by a fractional factorial design for the preliminary statistically significant parameters. The factors selected were extraction temperature, pressure, static extraction time, dynamic extraction time and carbon dioxide flow rate. The Doehlert design, followed by a multicriteria decision-making strategy, was then performed in order to determine the optimum conditions for the two most significant factors: pressure (165 bar) and dynamic extraction time (27 min). Under optimal conditions, the procedure developed with GC-MS/MS provides an excellent linearity, detection (0.01-0.2 ng g(-1)) and quantification limits (0.05-0.8 ng g(-1)) for most of the analytes investigated. The feasibility of the proposed supercritical fluid extraction method was validated by analysing two reference materials and fish feed and shellfish samples with satisfactory results.     

Spatial distribution and source apportionment of PCBs in sediments around İzmit industrial complexes, Turkey

The spatial distribution, degree of pollution and major sources of PCBs were evaluated in surficial sediments within the heavily urbanized and industrialized ?zmit Bay and its main freshwater inputs. ΣPCB concentrations range from 2.90 to 85.4ngg(-1) in marine sediments and from ND to 47.7ngg(-1) in freshwater sediments. Results suggest that high concentrations of ΣPCBs were localized around a chlor-alkali plant and an industry that handles bulk liquid, dry and drummed chemicals, and petroleum products in the Bay. Using a chemical mass balance receptor model (CMB), major sources of PCBs in the region were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources in marine sediments and the less chlorinated Aroclor 1248 and 1242 as the major PCB sources in freshwater sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.     

Accelerated delivery of polychlorinated biphenyls (PCBs) in recent sediments near a large seabird colony in Arctic Canada

Polychlorinated biphenyls (PCBs) were measured in sediment cores from ponds located near a large seabird colony at Cape Vera, Devon Island, Arctic Canada. Surface sediment PCB concentrations were ∼5× greater in seabird-affected sites relative to a nearby control pond and were correlated with independent indicators of seabird activity including, sedimentary δ¹⁵N and lakewater chlorophyll a and cadmium concentrations. PCB fluxes were amongst the highest recorded from the High Arctic, ranging from 290 to 2400 ng m⁻² yr⁻¹. Despite a widespread ban of PCBs in the mid-1970s, PCB accumulation rates in our cores increased, with the highest values recorded in the most recent sediments. Possible mechanisms for the recent PCB increases include a vertical flux step driven by seabird-delivered nutrients and/or delayed loading of PCBs from the catchment into the ponds. The high PCB levels recorded in the seabird-affected sites suggest that seabird colonies are exposing coastal ecosystems to elevated levels of contaminants.     

Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Determination of polychlorobiphenyls in Venice Lagoon sediments

Polychlorinated biphenyl (PCBs) congeners were measured in 14 sediment samples collected at five sites in the Venice Lagoon selected on the basis of a supposed diversity of inputs and of pollution levels. The PCBs were determined after a sonication assisted extraction by gas chromatography mass spectrometry (GCMS). The sum of the congener concentrations determined in the samples range from 4.05 to 239.15 ng/g on a dry weight basis. The concentration values are very variable both comparing the sites and comparing different samples from the same site and can be connected to the sand percentage in the sediment samples. The correlation matrix obtained from data matrix using the congener concentrations as variables shows high values, mostly between 0.964 and 1, suggesting that the pattern of the PCB congeners and the ratios among the concentrations in Venice Lagoon sediments are more or less constant; the samples differ only in the concentration level.     

Determination of potential sources of PCBs and PBDEs in sediments of the Niagara River

Sediments from Niagara River, an important waterway connecting two of the Great Lakes (Lake Erie to Lake Ontario), were analyzed for 14 congeners of polychlorinated biphenyls (PCBs) and 9 congeners of polybrominated diphenyl ethers (PBDEs) using accelerated solvent extraction and gas chromatography/mass spectrometry. Total concentrations of PCBs ranged from 1.7 to 124.6 ng/g were PCBs 138 and 153 were found in all samples. All sites but one showed PBDE in sediments with total concentrations as high as 148 ng/g, suggesting that PBDE is becoming an important class of POP. A land-use and coverage map was used to trace potential localized sources of PCB and PBDE contamination. Results indicate that the highest levels of PCBs and PBDEs were found in sediments collected from areas closest to the discharge locations of municipal wastewater treatment plants (WWTP) and local industries. This is the first study that suggests the importance of WWTP discharges as a potential source of PBDE contamination in the Great Lakes.     

Process-diagnostic patterns of chlorobiphenyl congeners in two radiochronologically characterized sediment cores from the northern Baffin Bay.

Polychlorinated biphenyl (PCB) patterns were interpreted in two radioisotopically constrained sediment cores from the Arctic ocean in order to seek clues about their large-scale environmental fates. Low but clearly measurable fluxes of individual PCB congeners were observed in deeper layer sediments, corresponding to the past 170 years, in a single dated core from the Baffin Bay shelf. Fluxes of the dominant individual congeners in the surface sediments were 20-100 pg m(-2) d(-1). Combining these data with the sediment data from the Arctic Monitoring and Assessment Program, it appears that the PCB distribution in Arctic surface sediments is governed by the organic carbon (OC) content of the sediments. The historical development of the PCB congener fingerprint suggests that the modern sediments are enriched in medium-chlorinated congeners, implying that there are at least two significant, but distinctly different, sink processes acting on the PCB pool. The relative abundance of light-to-heavy congeners, in mid-shelf marine sediments of similar ages, between 40 degrees N and 76 degrees N latitude suggests a northward dilution of PCBs which is stronger attenuated for heavier congeners, consistent with a temperature-driven global fractionation process. The significant presence of PCB in historical archives pre-dating the organochlorine society, as observed in this and several previous studies, awaits a fuller explanation.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.