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.     

Persistent chlorinated pesticides and polychlorinated biphenyls in selected fish species from Lake Tanganyika, Burundi, Africa

Concentrations of selected organochlorine pesticides and PCBs in seven fish species (cichlids) from the north end of the Lake Tanganyika, Burundi, Africa were determined. Results were compared to previous work on the Lake Tanganyika and other water bodies and to the European Community maximum residue levels (MRLs) in edible fat. The analytical method included a hot Soxhlet extraction with a mixture of acetone: hexane (1:3, v/v), gravimetrically lipid determination, and a single step clean-up. For PCBs and stable pesticides, the clean-up was done on activated silica gel impregnated with concentrated sulfuric acid, while for non acid-stable pesticides superposed layers of alumina, silica and florisil impregnated with 15% methanolic solution of KOH were successively used. Recoveries of organochlorine pesticides from certified reference material (CRM 430) were ranging from 86% for p,p'-DDT to 107% for endrin, while recoveries from blank fat spiked fortified at three different levels were between 65% for alachlor at the lowest fortification level and 107% for mirex at the highest fortification level. The limits of detection for each analyte were ranging from 0.1 ng/g to 0.5 ng/g fat. All chlorinated pesticides were found in the analyzed species but at low concentrations. Boulengerochromis microlepis contained the highest concentrations of HCHs (288.2 +/- 15.5 ng/g fat) and DDTs (909.1 +/- 42.5 ng/g fat), while the highest PCB levels (166.7 +/- 37.4 ng/g fat for the sum of 12 congeners) were found in Oreochromis niloticus. However, there is no evidence that Lake Tanganyika is more contaminated with pesticides than other African water bodies.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Fatty acid profile and elemental content of avocado (Persea americana Mill.) oil--effect of extraction methods

Interest in vegetable oil extracted from idioblast cells of avocado fruit is growing. In this study, five extraction methods to produce avocado oil have been compared: traditional solvent extraction using a Soxhlet or ultrasound, Soxhlet extraction combined with microwave or ultra-turrax treatment and supercritical fluid extraction (SFE). Traditional Soxhlet extraction produced the most reproducible results, 64.76 ± 0.24 g oil/100 g dry weight (DW) and 63.67 ± 0.20 g oil/100 g DW for Hass and Fuerte varieties, respectively. Microwave extraction gave the highest yield of oil (69.94%) from the Hass variety. Oils from microwave extraction had the highest fatty acid content; oils from SFE had wider range of fatty acids. Oils from Fuerte variety had a higher monounsaturated: saturated FA ratio (3.45-3.70). SFE and microwave extraction produced the best quality oil, better than traditional Soxhlet extraction, with the least amount of oxidizing metals present.     

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.     

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France)

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). summation operator2,3,7,8-PCDD/F and summation operator7ICES PCB air concentrations (0.2-1.4 and 31-57pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476fg L(-1)) and low for PCBs (138-708pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33ng g(-1) d.w., respectively) and mussel (13-21pg g(-1) d.w. and 10-39ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.     

Organochlorinated contaminants in decapod crustaceans from the coasts of Brittany and Normandy (France)

The contamination and distribution of organochlorinated compounds were considered in three crustacean species (edible crab, Cancer pagurus; spider crab, Maja brachydactyla; velvet swimming crab, Necora puber) from five sites along the coasts of Brittany and Normandy (Western and North-Western France). PCBs (16 single congeners), pp'-DDE and HCB were measured in hepatopancreas, gonads and muscle: in all, 175 samples were analysed. The spider crab was the only species found in the five sampling sites, thus enabling comparison between areas. Specimens from Antifer were much more contaminated (summation operator 16 PCBs in hepatopancreas=2000-4000 ng g(-1) dry weight) than those from other sites (50-1000 ng g(-1) d.w.). Among all the three species, the spider crab appeared more contaminated by PCBs than the edible crab, by a factor 2-3, probably in relation with specific differences in their life cycle. There was no difference due to the gender of the species. Within the different analysed tissues, contamination levels increased from muscle to gonads and hepatopancreas in relation with the fat content. A very similar PCB composition was observed in all samples, PCB fingerprints being characterised by the relative importance of the more persistent PCB congeners: CB153, 138, 180, 187, and 118. Finally, these results were compared to recent food regulations first of maximum marker PCB intake and secondly of maximum dioxin-like PCB intake. By considering the muscle, all samples were far below the regulatory limits; for hepatopancreas and gonads, however, some samples were unfit for human consumption.     

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.     

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.     

Vertical fluxes and accumulation of PCBs in coastal sediments of the Río de la Plata estuary, Argentina

Settling particles and underlying sediments collected at 1, 2.5 and 4 km along offshore transects in the urbanized sector of the Río de la Plata were analyzed to evaluate the sources and accumulation of PCBs. Total PCB concentrations range from <0.1 to 100 ng g(-1) and include variability associated to North-South and offshore gradients reflecting the impact of coastal discharges. Highest concentrations were recorded in the industrialized Central area close to Buenos Aires (61+/-37 ng g(-1) at 1 km) relative to cleaner northern stations (3.6+/-2.2 ng g(-1)) and southward sites (37+/-2.8 ng g(-1)), affected by transport of particulate PCBs by coastal currents. Sediment traps deployed in the Central area revealed large depositional fluxes of total matter (361+/-124 gm(-2)day(-1)) and PCBs (26+/-19 microg m(-2)day(-1)) and high sedimentation rates (5.0+/-1.7 cm yr(-1)). Uniform PCB concentrations (66-89 ng g(-1)) down to 20 cm in sediment cores suggest continued PCB discharges during the last 4 years. PCB composition was dominated by hexa (43+/-6.4%), hepta (23+/-5.1%) and pentachlorobiphenyls (21+/-5.5%) with lower proportions tri-tetra (7.4+/-5.4%) and higher chlorinated congeners (5.1+/-3.3%). A consistent weathering pattern with loss of 3-5 chlorobiphenyls and enrichment in higher chlorinated PCBs corresponding to a shift from a 1:1 to a 1:3 1254:1260 Aroclor mixture, was observed offshore. A principal component analysis performed with the relative contribution of PCB congener classes confirmed the offshore weathering pattern indicating that transformer oils containing Aroclor 1254-1260 are the most probable sources. Sediment inventories, sediment trap fluxes and Fugacity II calculations indicate an accumulation approximately 500-800 kg PCB in superficial sediments of this coastal environment.     

Pesticide contamination profiles of water, sediment and aquatic organisms in the effluent of Gaobeidian wastewater treatment plant

Organochlorine pesticides (OCPs, including DDT, HCH and HCB) and six indicator polychlorinated biphenyls (PCB 28, 52, 101, 138, 153, and 180) were measured in water, sediment, zooplankton, fish and Chinese softshell turtle (Pelodiscus sinensis) from Gaobeidian Lake, which is located in the effluent of Gaobeidian wastewater treatment plant (WWTP) in Beijing, China. DDTs were dominant except for in water. In water, the concentrations of DDTs (6.22 ng l(-1)) and HCHs (18.0 ng l(-1)) were less than the limits (l000 ng l(-1) for DDTs and 5000 ng l(-1) for HCHs). However, PCBs concentration (20.8 ng l(-1)) exceeded the limit (14 ng l(-1)) suggested by the United States Environmental Protection Agency (USEPA). The high ratio of p,p'-DDT/DDTs (0.80) in water suggested that DDTs had recently been discharged into the ambient environment despite a longtime ban in China. For fish and Pelodiscus sinensis, the accumulation patterns of OCPs and PCBs were different in muscle and liver. And HCB and PCB 153 were significant different in different species (p<0.05). PCBs were dominated by PCB 52 in zooplankton, but by PCB 138 and 153 in Pelodiscus sinensis. The highest food web magnification factor (FWMF) was 4.83 for p,p'-DDT and the second highest was 4.36 for PCB 101 in Gaobeidian Lake. As compared with the other studies, biomagnification in the present study was not obvious. Trophic levels and age were two important factors that might contribute to the bioaccumulation in the present study.     

PCBs and HCHs in a salt-marsh sediment record from South-Central Chile: use of tsunami signatures and 137Cs fallout as temporal markers

This paper documents the occurrence of polychlorinated biphenyl (PCB) and hexachlorocyclohexane (HCH) deposition inferred from a sedimentary record exposed in a salt-marsh trench in South-Central Chile. Sediments were carefully collected every 1 cm from the trench wall. The samples were analyzed for PCBs, HCHs, 137Cs, organic carbon and grain size. The 137Cs fallout and the sedimentary signature left by the 1960 Chilean tsunami were used as temporal markers to estimate the stratigraphic chronology and the sedimentation rates. PCBs were quantified by gas chromatography with electron capture detection (GC-ECD), and positive samples were confirmed by gas chromatography and mass spectrometry detection (GC-MS). Based on these results, PCBs and HCHs deposition over the last 40 years was estimated. No PCBs were detected below the tsunami signature. Total concentrations ranged from undetectable (ND) to 32 ng/g d.w. for PCBs and from undetectable (ND) to 1.29 ng/g d.w. for HCHs. The highest PCB concentrations were found in the upper 7 cm of the core. Even though PCBs were banned in 1982 as electrical fluids in Chile, total estimated PCB fluxes have increased approximately 20 times during the last 40 years: from undetectable values to 102.6 ng/cm2/year, reflecting that PCBs are still in use and being released into the environment.     

Comparative study of methodologies for the analysis of PCDDs and PDCFs in powdered full-fat milk. PCB, PCDD and PCDF levels in commercial samples from Spain

Feasibility of two different extraction methods involving solid-liquid extraction and Soxhlet extraction, previously used for the determination of lipid contents and PCB levels on powdered full-fat milk, are now examined for simultaneous PCDD/F analysis. The results of this study are consistent with those found for PCBs. The solid-liquid procedure provides the most efficient extraction of both labelled spiked and endogenous PCDD/Fs with the lowest variability. The average recoveries were 101% (R.S.D. = 6.9%) for 13C12-2,3,7,8-TCDD and 95% (R.S.D. = 11%) for 13C12-1,2,3,4,7,8-HxCDD. The R.S.D.s for endogenous 2,3,7,8-PCDD/Fs were in the 9.3-25% range. In addition, this methodology simplified the subsequent clean-up step as it allowed a semi-selective extraction of the apolar lipids from the milk. The proposed method was applied to simultaneous PCB and PCDD/F analyses in different brands of powdered full-fat milks commercially available in Spain. In all cases, very similar PCB and PCDD/F levels were found. Differences among batches from the same manufacturer were even lower. The total i-TEQ average for PCDDs and PCDFs in the 22 powdered full-fat milk samples analysed was 1.87 pg/g fat basis. This value was similar to those found in cow's milk from other European countries.     

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.     

Feeding trial on rainbow trout: comparison of dry fish feed and Baltic herring as a source of PCDD/Fs and PCBs

Fish is an important source of dietary intake of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). To assess bioaccumulation of PCDD/Fs and PCBs in farm-raised fish, rainbow trout were fed with either Baltic herring or dry fish feed. Baltic herring feed had a PCDD/F sum concentration of 125 ng kg(-1) dry weight (d.w.), and dry fish feed contained 18.2 ng kg(-1) d.w. of PCDD/Fs. The PCB concentrations of Baltic herring and dry fish feed were 188 and 48.7 microg kg(-1) d.w., respectively. After feeding with Baltic herring for 4 months, the PCDD/F concentration of the rainbow trout fillet was 27.3 ng kg(-1) fresh weight (f.w.), which was 7.0-fold higher than the initial concentration. The PCDD/F concentration and congener profile in rainbow trout had become almost the same as in Baltic herring. PCDD/Fs were accumulated in the fillet with an efficiency of 21%. Feeding of rainbow trout with dry fish feed resulted in a PCDD/F concentration of 8.08 ng kg(-1) f.w., denoting a 2.1-fold increase from the initial level. The accumulation efficiency was 29%. Time trends in PCB concentrations followed those of PCDD/Fs. After 4 months, the PCB sum concentration in herring-fed rainbow trout was 94.4 pg kg(-1) f.w., whereas in dry fish feed-fed rainbow trout it was 38.6 microg kg(-1) f.w. Accumulation efficiencies of PCBs were higher than those of PCDD/Fs. Based on the accumulated PCDD/F and PCB concentrations, it was estimated that frequent consumption of rainbow trout fed with Baltic herring could lead to a human daily intake that exceeds the recommendation of WHO.     

Digestibility, retention and incorporation of low-level dietary PCB contents in laying hens

Polychlorinated biphenyls (PCBs) are persistent and hazardous environmental contaminants, which tend to bioaccumulate in the food chain. In the present report the long-term effect of low-level dietary PCB concentrations was studied on performance, egg quality, apparent PCB digestibility, apparent PCB retention and PCB accumulation in laying hens that were fed experimental diets for 41 weeks. The tested dietary concentrations of supplemented PCBs, based on the sum of seven reference congeners, were 0, 1.5 and 6 ng/g. PCB ingestion did not significantly affect performance or egg quality parameters. The PCB concentration in egg yolk reached a nearly constant level after approximately 40 and 70 days of consumption of the diets containing 1.5 and 6 ng PCBs/g, respectively. Apparent faecal PCB digestibility and apparent retention were not influenced by dietary levels of added fat varying between 1.5% and 4.5%, but were significantly higher in hens fed diets containing added PCBs. Moreover, apparent PCB digestibility and retention increased significantly with age. Among the seven individual PCB congeners, no systematically significant differences with regard to apparent faecal digestibility were observed throughout the experiment. Accumulation of PCBs in the fat fraction of egg yolk, abdominal adipose tissue and thigh and breast muscle greatly depended upon PCB intake, but never exceeded the maximally allowed concentration of 200 ng/g. As PCBs 52 and 101 were hardly found in egg yolks and hen tissues, it was concluded that both congeners were greatly metabolised. Comparison of relative contents of individual PCB congeners revealed that PCBs 118, 138 and 153 were preferentially incorporated in yolk and body tissues.     

Fatty acid profile and elemental content of avocado (Persea americana Mill.) oil –effect of extraction methods

Interest in vegetable oil extracted from idioblast cells of avocado fruit is growing. In this study, five extraction methods to produce avocado oil have been compared: traditional solvent extraction using a Soxhlet or ultrasound, Soxhlet extraction combined with microwave or ultra-turrax treatment and supercritical fluid extraction (SFE). Traditional Soxhlet extraction produced the most reproducible results, 64.76 ± 0.24 g oil/100 g dry weight (DW) and 63.67 ± 0.20 g oil/100 g DW for Hass and Fuerte varieties, respectively. Microwave extraction gave the highest yield of oil (69.94%) from the Hass variety. Oils from microwave extraction had the highest fatty acid content; oils from SFE had wider range of fatty acids. Oils from Fuerte variety had a higher monounsaturated: saturated FA ratio (3.45–3.70). SFE and microwave extraction produced the best quality oil, better than traditional Soxhlet extraction, with the least amount of oxidizing metals present.     

Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

Distribution of polychlorinated biphenyls and polybrominated diphenyl ethers in birds of prey from Switzerland

Polychlorinated biphenyls (PCBs) and the structurally related polybrominated diphenyl ethers (PBDEs) have been associated with chronic neurotoxicity involving reduced motor activity and impaired attentiveness. Such neurobehavioral effects indicate that the central nervous system may represent an important target organ for the action of these persistent contaminants in wildlife. As a consequence, the brain of different terrestrial and aquatic birds collected in Switzerland was analysed for PCBs and PBDEs. In parallel, the same contaminants were examined in the accompanying adipose tissue. After clean-up by means of glass columns containing acidified silica, deactivated alumina and anhydrous sodium sulphate, the samples were analysed by high resolution gas chromatography/tandem mass spectrometry (HRGC-MS/MS). Median PCB concentrations in the brain (sum of PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) ranged between 13 ng g(-1) wet weight (ww) in blackbirds (Turdus merula) and 428 ng g(-1) ww in sparrow hawks (Accipiter nisus). Median PBDE concentrations in the brain (sum of BDE 28, BDE 47, BDE 99, BDE 100, BDE 153, BDE 154 and BDE 183) ranged from below the decision limit in buzzards (Buteo buteo) and blackbirds, to 14 ng g(-1) ww in sparrow hawks. After correction for the respective lipid content, higher PCB or PBDE concentrations in brain compared to adipose tissue, were found in three sparrow hawks, four buzzards and in all investigated blackbirds. These results suggest that a deficit in the neuroprotective function of the blood-brain barrier may cause unexpected levels of PCBs and PBDEs in the central nervous system.     

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.