Levels of polychlorinated biphenyls in the lower troposphere of the North- and South-Atlantic Ocean

Summary Fourteen polychlorinated biphenyl (PCB) congeners were quantified in air samples of the tropospheric boundary layer of the Atlantic Ocean. The samples were taken on the German research vessel Polarstern during north-south cruises across the Atlantic Ocean (1990, 1991), and on the Capo Verde islands in the North Atlantic Ocean (1992). Values for the sum of PCB were between 48 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 1.3; PCB 52: 5.0; PCB 101: 3.0; PCB 118: 0.5; PCB 138: 1; PCB 153: 1; PCB 180: <0.2) in the Westwind Belt of the eastern North Atlantic and 22 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.3; PCB 52: 3.4; PCB 101: 0.5; PCB 118: <0.2; PCB 138: <0.2; PCB 153: <0.2; PCB 180: <0.2) in the Westwind Belt of the central South Atlantic. Up to 385 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.6; PCB 52: 11.7; PCB 101: 28.4; PCB 118: 9; PCB 138: 21; PCB 153: 18; PCB 180: 5.5) were measured of the coast of South Patagonia. A difference depending on latitude and on terrestrial influenced air masses between the lower and the higher chlorinated congeners was observed. The levels of three- and tetrachlorinated congeners were highest in the Trade Wind regions. The contents of the higher chlorinated congeners had maxima in samples influenced by continental air masses. A correlation of the levels of the lower chlorinated congeners in air over the South Atlantic with the surface water temperature and thus with the temperature dependent gas/water partition coefficient K_gw was observed. Part XVI: Fischer RC, Krämer W, Ballschmiter K (1991) Chemosphere 23:889–900     

A rapid screening method for routine congener-specific analysis of polychlorinated biphenyls in human serum by high-resolution gas chromatography with mass spectrometric detection

A screening method using gas chromatography/mass spectrometry in the single ion monitoring (SIM) mode for the routine congener-specific analysis of polychlorinated biphenyls (PCBs) in human serum has been developed and validated. A fast procedure incorporating both liquid-liquid and solid-phase extraction was used for clean up and enrichment. Interday and intraday precision and accuracy were assessed for the 12 congeners having dioxin-like activity and PCBs #180 and #170 by analyzing spiked samples on three subsequent days and using (13)C(12)-labelled analogues as internal standards. Furthermore, the relative errors for six non-dioxin-like congeners (PCBs #28, #52, #101, #138, #153 and #180) were measured by using certified reference materials, providing good accuracy at two different concentration levels. The limits of quantification and of detection were 0.5 and 0.2 micro g/L in serum for each congener, respectively. The method allows the chromatographic separation of at least 35 congeners and can therefore be applied to the routine monitoring of the general population for both dioxin-like and non-dioxin-like PCB congeners.     

Dispersive liquid-liquid microextraction followed by gas chromatography–electron capture detection for determination of polychlorinated biphenyls in fish

A new method of dispersive liquid-liquid microextraction (DLLME) combined with GC-electron capture detection (GC-ECD) was proposed for the extraction and determination of four polychlorinated biphenyls (PCBs) congeners in fish samples. Acetone was used as extraction solvent for the extraction of PCBs from fish samples. The target analytes in the acetone solvent were rapidly transferred to chlorobenzene, which was used as extraction solvent in DLLME procedures. Under the optimum conditions, linearity was obtained in the concentration range from 1.25 to 1250 μg/kg for PCB 52, and 0.25 to 250 μg/kg for PCB 101, 138 and 153. Coefficients of correlation (r²) ranged from 0.9993 to 0.9999. The repeatability was tested by spiking fish samples at 10 μg/kg PCBs, and RSD% (n = 8) varied between 2.2 and 8.4%. The LODs were between 0.12 and 0.35 μg/kg. The enrichment factors of PCBs were from 87 to 123. The relative recoveries of the four PCB congeners for the perch, pomfret and yellow-fin tuna at spiking levels of 10, 20 and 50 μg/kg were in the range of 81.20–100.6%, 85.00–102.7% and 87.80–108.4%, respectively. The results demonstrated that DLLME combined with GC-ECD was a simple, rapid, and efficient technique for the extraction and determination of PCBs in fish samples.     

Gas chromatography/mass spectrometry of polychlorinated biphenyls using atmospheric pressure chemical ionization and atmospheric pressure photoionization microchips

Gas chromatography (GC) and ion trap mass spectrometry (MS) were combined with microchip atmospheric pressure chemical ionization (microAPCI) and microchip atmospheric pressure photoionization (microAPPI) sources. Selected polychlorinated biphenyls (PCBs, IUPAC Nos. 28, 52, 101, 118, 138, 153 and 180) were analyzed by GC/microAPCI-MS and GC/microAPPI-MS to demonstrate the applicability of the miniaturized ion sources in negative ion mode analysis. The microAPCI and microAPPI methods were evaluated in respect of detection limit, linearity and repeatability. The detection limits for the PCB congeners were somewhat lower with microAPCI than with microAPPI, whereas microAPPI showed slightly wider linear range and better repeatability. With both methods, the best results were obtained for highly chlorinated or non-ortho-chlorinated PCBs, which possess the highest electron affinities. Finally, the suitability of the GC/microAPPI-MS method for the analysis of PCBs in environmental samples was demonstrated by analyzing soil extracts, and by comparing the results with those obtained by gas chromatography with electron capture detection (GC/ECD).     

Determination of mono- to octachlorobiphenyls in fish oil using florisil adsorption followed by headspace solid-phase microextraction and gas chromatography with time-of-flight mass spectrometric detection

A simple and reliable method for the determination of polychlorinated biphenyls (PCBs) from mono- to octachlorobiphenyls in fish oil for dietary supplement is described. The method combines Florisil clean up and headspace solid-phase microextraction on 65 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB). Analyte detection was carried out using GC-time-of-flight mass spectrometry (GC-TOF-MS). Fifty three PCB congeners including the seven indicator PCBs (IUPAC Nos. 28, 52, 101, 118, 138, 153 and 180) were analyzed. Under optimal conditions, the method detection limit (MDL) of each congener in the range from 0.8 to 31 ng/g was found. A certified reference material (BCR-349) was analyzed and it showed good agreement with the certified data.     

Chiral comprehensive two-dimensional gas chromatography with electron-capture detection applied to the analysis of chiral polychlorinated biphenyls in food samples

The feasibility of comprehensive two-dimensional gas chromatography with electron-capture detection (GC x GC-ECD) for the enantioseparation of chiral PCBs from other possible interfering compounds has been evaluated. Three commercially available enantioselective beta-cyclodextrin-based capillary columns (Chirasil-Dex, BGB-172 and BGB-176SE) have been tested as first-dimension columns. Three non-enantioselective stationary phases (HT-8, BPX-50 and Supelcowax-10) were combined with the enantioselective columns to allow the unambiguous determination of the enantiomers of the target chiral PCBs. Each enantioselective first-dimension column tested was able to separate into enantiomers different PCB congeners, but in all cases, the use of Supelcowax-10 as second-dimension column provided the most satisfactory results. The Chirasil-Dex x Supelcowax-10 column combination allowed the determination of the enantiomeric fraction (EF) of PCBs 84, 91, 95, 132, 136, 149, 174 and 176 in the working standard solution, while that of congener 135 was hindered. The BGB-172 x Supelcowax-10 column set allowed a proper EF determination of congeners 45, 84, 131, 132, 135, 171, 174 and 183, while that of PCB 91 was interfered with co-elutants. The column combination BGB-176SE x Supelcowax-10 allowed the determination of all congeners that this enantioselective stationary phase was able to separate into enantiomers, i.e. PCBs 45, 91, 95, 136, 149 and 176. These column combinations have also been evaluated for the simultaneous determination of the 12 congeners with a toxic equivalency factor assigned by the WHO (PCBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) and the seven indicator congeners (PCBs 28, 52, 101, 118, 138, 153 and 180), and evaluated for the analysis of food samples.     

Multidimensional capillary gas chromatography of polychlorinated biphenyl marker compounds

Multidimensional chromatography was used to resolve the specific chlorobiphenyl (CB) congeners 28, 52, 101, 118, 138, 153, and 180 in technical aroclor standards. Single column analysis of polychlorinated biphenyls (PCBs) results in co-elution of key congeners with other components in the mixture; therefore using two columns of different selectivity was necessary to enhance the resolution achievable on just one column. The HT8 column (8% phenylpolycarborane-siloxane phase) has been reported to have specific selectivity characteristics for improved PCB separation. When coupled with a BPX5 column (5% phenylpolysiloxane-silphenylene phase), it has been shown here to provide unambiguous identification of 7 marker compounds which are used to monitor PCB occurrence and distribution. All seven marker CBs are present in aroclor 1254, and by adjusting the size of the heartcut window, it was possible to obtain resolution of the marker congeners from other congeners. Single column analysis is unable to achieve this result. This offers an alternative to GC-MS analysis.     

Polychlorinated biphenyls,dibenzo-p-dioxins and dibenzofurans in soil samples from airport areas of Croatia

Levels and patterns of polychlorinated biphenyls (PCBs) were studied in surface soil samples collected in the coastal part of Croatia within and surrounding four different airports and in the vicinity of two partially devastated electrical transformer stations. The compounds accumulated from air-dried soil samples by multiple ultrasonic extraction with an n-hexane?:?acetone 1?:?1 mixture were analysed by capillary gas chromatography with electron capture and ion-trap detection. PCBs were quantified against a standard Aroclor 1242/Aroclor 1260 mixture and a standard mixture of 17 individual PCB congeners (IUPAC No.: 28, 52, 60, 74, 101, 105, 114, 118, 123, 138, 153, 156, 157, 167, 170, 180, and 189). The mass fractions of total PCBs in 18 soil samples collected within the airport premises ranged from 3 to 41?327?µg/kg dry weight (dw) (median: 533?µg/kg?dw), and those in 21 samples collected at a distance ranging from several metres to 5?km away from the airport fence, from <1 to 39?µg/kg?dw (median: 5?µg/kg?dw). The highest PCB levels were determined in soils along the airport aprons where the aircrafts were serviced and refuelled. The PCB pattern was very similar to technical Aroclor 1260 in all airport soils. The PCB pattern in 22 soils collected in the vicinity of electrical transformer stations was dominated by congeners contained in Aroclor 1242. These soils contained 7 to >400?µg/kg?dw of total PCBs. One highly PCB-contaminated airport soil sample was analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). With an international toxic equivalent (I-TEQ) of 9.7?ng/kg?dw, the airport soil contamination was within values typical for urban and rural areas, and the congener patterns gave no clear indication for PCBs as the only source of PCDDs/PCDFs.     

Rapid Chromatography for the Determination of Polychlorinated Biphenyls by GC-MS in Environmental Monitoring

A method for determination of polychlorinated biphenyls (PCBs) in environmental and biological materials has been developed. This method includes rapid chromatography requiring less than 10 min using an HT-8 capillary column at 30 m × 0.25 mm i.d. Rapid chromatography was performed using a column temperature gradient from 80 to 310°C at a rate of 40°C/min. Low-resolution mass spectrometry in single ion monitoring mode of simultaneous detection of 12 target ions is suggested for detection of PCBs peaks. The method not only enabled us to reduce time of analysis but also to increase the efficiency of separating PCB peaks from interferences and to reduce levels of detection of analytes resulting in a minimized sample preparation stage. The last includes extraction of the PCBs using organic solvents, preliminary alkaline hydrolysis in the case of biological objects, and cleaning up the extracts on compact cartridges. The method was tested in monitoring studies for these contaminants in soils, sediments, snow cover, fish tissues, and seal blubber. Total PCBs and isomer congener groups of the same chlorination degree and seven indicator congeners (IUPAC No.'s 28, 52, 101, 118, 138, 153, and 180) are determined with a high degree of certainty. The PCB concentrations were in the range of 1–700 ng/g dry weight for environmental samples and 500–25000 ng/g lipids for biota. The method yields measurements of total PCBs and isomer groups with a precision no greater than 10% and no greater than 15% for the indicator congeners.     

Enhanced comprehensive two-dimensional gas chromatographic resolution of polychlorinated biphenyls on a non-polar polysiloxane and an ionic liquid column series

A total of 196 out of 209 polychlorobiphenyl (PCB) congeners were resolved using GC×GC-TOFMS with a non-polar/ionic liquid column series consisting of poly(50%-n-octyl-50%-methyl)siloxane and (1,12-di(tripropylphosphonium)dodecane bis(trifluoromethansulfonyl)amide) in the first and second dimension, respectively. It has been found that 13 PCB congeners overlap in five doublets (CB12+CB13, CB62+CB75, CB70+CB76, CB97+CB125 and CB153+CB168) and one triplet (CB90+CB101+CB113). All toxic, "dioxin like" congeners were separated with no interferences from any PCB congener. The 109 PCBs present in Aroclor 1242 and the 82 PCBs present in Aroclor 1260 were resolved GC×GC-TOFMS analysis on this column set.     

Serum organochlorine pesticide and polychlorinated biphenyl levels measured in delivering women from different locations in Tunisia

Blood serum concentrations of polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) such as dichlorodiphenytrichloroethane and its metabolites (DDTs), hexachlorobenzene (HCB) and hexachlorocyclohexane isomers (HCHs) were measured in maternal serum (n = 82) from mothers living in different regions in Tunisia. Gas chromatography with electron capture detection was used to quantify residue levels on a volume basis of the organochlorine compounds (OCs). The pattern of OCP in human serum showed that DDTs was consistently the prevalent OC in blood. p,p′-DDE, the major metabolite of p,p′DDT, and HCB were found in all serum samples with mean concentrations of 1.69 and 0.42 ng mL^?1, respectively. PCB congeners 138, 153 and 180 were the predominant congeners measured in all serum samples with a detection frequency of 80%, 72% and 83%, respectively. In general, results found in the investigated group are lower than the concentrations measured in serum blood in other countries.     

Determination of polychlorinated biphenyls by fast chromatography mass-spectrometry in environmental and biological samples

A method for the determination of polychlorinated biphenyls (PCB) by fast gas chromatography coupled with mass-spectrometric detection in selective ion monitoring mode has been developed. Chromatographic separation was carried out with HT-8 column (30 m × 0.25 mm) under sharp temperature increase from 80 to 320°C at a rate of 40°C/min. Duration of chromatography is 10 min. Fast chromatography conditions suggested by authors makes it possible to increase S/N ratios 10 times and so to reduce significantly the representative weight of the sample and develop an effective sample preparation technique. The method was used for PCB determination in Baikal area samples such as soil, snow, sediments from Lake Baikal and its tributaries, tissues of Baikal omul (Coregonus migratorius, Georgi, 1775) and blubber of Baikal seal (Phoca sibirica Gm.). The sample preparation stage includes PCB extraction from environmental samples and hydrolyzate of biological material with the following cleanup of the extract on the compact silica gel and florisil cartridges (0.5 g of the sorbent). The method enables the measurements of total PCBs and isomer groups of the same chlorination level with interlaboratory precision of no greater than 10% and the determination of indicator congeners (PCBs 28, 52, 101, 118, 138, 153, and 180) with a precision not exceeding 15%.     

Reactivity features of polychlorobiphenyl congeners in the nucleophilic substitution reactions

Groups of congeners and individual congeners of polychlorobiphenyls contributing to the composition of the technical mixture “Sovol” (PCB 60, PCB 64, PCB 70, PCB 74, PCB 97, PCB 101, PCB 105, PCB 110, PCB 118, PCB 138, PCB 149, PCB 156, and PCB 163) were synthesized by the reaction of aryl-aryl coupling. The interaction of the congeners with sodium methoxide was performed and their complete conversion was proved. By means of gas chromatography-mass spectrometry the PCBs methoxy derivatives were identified. The data on the reactivity of the individual polychlorobiphenyl congeners were precised.     

Congener profile and toxicity assessment of polychlorinated biphenyls in human adipose tissue of Italians and Chileans

Human exposure to polychlorobiphenyls (PCBs) in humans was determined by analyzing adipose tissue samples collected in 1996–1997 from two different localities: Siena (Italy) and Concepción (Chile). ΣPCBs was higher in Italian samples than that from Chile (493 and 53 ng/g wet wt., respectively). Thirty-seven different PCB congeners were identified in all samples. The prevailing PCB congeners in both groups were 22′44′5 pentachlorobiphenyl (IUPAC no. PCB 118), 22′344′5′ (PCB-138) and 22′44′55′ (PCB-153) hexachlorobiphenyls and 22′33′44′5 (PCB-170), 22′344′55′ (PCB-180) and 22′34′55′6 (PCB-187) heptachlorobiphenyls. PCB-153 accounted for more than 20% of the total PCB residue in both groups, while the remaining six congeners accounted for approximately 70%. Hexachlorobiphenyls were the most abundant congeners in all samples, with 42% of total residue in those from Italy and 43% in the Chilean samples, followed by heptachlorobiphenyls with 41 and 36% in Italian and Chilean samples, respectively. Average concentrations of non-ortho substituted coplanar congeners were below 1 pg/g wet wt. In the samples from Siena no noticeable differences were observed between the three average coplanar concentrations, while in those from Concepción 33′44′tetrachlorobiphenyl (PCB-77) was much higher than 33′44′pentachlorobiphenyl (PCB-126) and 33′44′55′hexachlorobiphenyl (PCB-169). For each sample the contribution to the total toxic equivalent values (ΣTEQs) of each non-ortho, mono-ortho and di-ortho substituted PCB congeners was assessed. The overall TEQs calculated for the monitored PCBs, were 10.16 pg/g wet wt. in Italian samples and 1.09 pg/g wet wt. in Chileans ones. In both groups the main contribution to ΣTEQs were the di-ortho substituted PCB congeners (Siena: 6.17 pg/g wet wt.; Concepción: 0.56 pg/g wet wt.) and the mono-ortho substituted PCB congeners (Siena: 3.97 pg/g wet wt.; Concepción: 0.50 pg/g wet wt.).     

Characterization of Losses of Chlorinated Pollutants during Lyophilization of Mussels

The influence of the lyophilization process on the recovery of ten organochlorine compounds, (9 polychlorinated biphenyls (PCBs) and pp′-DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene)] during the pretreatment step of mussels was studied at three concentration levels. Losses of more polar and water-soluble compounds were approximately 50% in samples pulverized prior to lyophilization. Two variables, moisture and lipid concentrations, had statistical influences in the losses of the lower chlorinated compounds (CB 31 and CB 28). In some PCB congeners (CB 52, CB 101, and CB 118), the variation of losses with the PCB concentrations was also statistically significant.     

Application of a retention database to the identification of individual polychlorinated biphenyl congeners in Aroclors mixture using selected polychlorinated biphenyls as a reference series

The database of the relative retention times (RRTs) of polychlorinated biphenyls (PCBs) reported in literature was used to calculate the retention indices (RIs) of all 209 PCB congeners on temperature programmed capillary column Rtx-5. Calculation of retention indices was based on reference series of seven congeners (PCB IUPAC Nos. 18, 52, 101, 143, 185, 203 and 206) that exhibit linear relative retention time behaviour as a function of chlorine number. The calculated indices were compared to those determined in our laboratory as well as to those obtained by other authors. The proposed indices system was applied for identification individual congeners in mixture of Aroclors 1242:1254:1260, using only reference series of PCBs.     

Ultrasound‐assisted magnetic SPE based on Fe3O4‐grafted graphene for the determination of polychlorinated biphenyls in water samples

An ultrasound‐assisted magnetic SPE procedure with an Fe₃O₄‐grafted graphene nanocomposite as the magnetic adsorbent has been developed to determine seven polychlorinated biphenyls (PCBs; PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, and PCB180) simultaneously in 200 mL environmental water samples, in combination with GC–MS/MS. Several factors related to magnetic SPE efficiencies, such as the superparamagnetic intensity and amount of adsorbent, extraction time, sample pH, and desorption conditions were investigated. With the assistance of ultrasound, the extraction achieved the maximum within only 20 s, attributed to the powerful adsorptive ability of the magnetic adsorbent toward the PCBs. Under the optimized conditions, an excellent linearity was observed in the range of 0.1–100 ng/L for PCB28, 0.2–100 ng/L for PCB52, and 0.5–100 ng/L for the other five PCBs with the correlation coefficients ranging from 0.9988 to 0.9996. The mean recoveries at spiked levels of 5.0 and 10.0 ng/L were 84.9–108.5%, the coefficients of variations were <6.5%. With convenient magnetic separation, the synthesized magnetic adsorbent could be recycled more than ten times. The proposed method was demonstrated to be feasible, simple, rapid, and easy to operate for the trace analysis of the PCBs in environmental water samples.     

Intercomparison on measurements of PCBs in pork fat during the Belgian PCB-crisis

During the Belgian PCB crisis (1999/2000) the quality of the data from the PCB monitoring were studied with a proficiency testing experiment. Pork fat that was spiked at the Institute for Reference Materials and Measurements (EC-JRC-IRMM) was sent out as unknown to all laboratories that participated in the monitoring. In parallel, the material was certified on the basis of the results of several leading PCB laboratories throughout Europe that did not participate in the monitoring. During the first round 15 to 25% deviation was experienced, while in the end of this multistep intercalibration procedure the average deviation for the respective PCBs was 10.9% (PCB 28), 13.1% (PCB 52), 10.1% (PCB 101), 10.7% (PCB 118), 10.7% (PCB 138), 9.1% (PCB 153), 8.1% (PCB 180) and 8.2% for the sum of the 7 PCBs. The concentrations measured for the higher volatile PCB 28 had a tendency to show lower levels, while for PCB 180 this was less pronounced. On the other hand, PCB 153 showed results rather to the higher side. During this exercise the material was also tested for stability by one of the certifying laboratories.     

Determination of Indicator Congeners of Polychlorinated Biphenyls in Water at Ultratrace Levels by Gas Chromatography–Tandem Mass Spectrometry

Journal of Analytical Chemistry - We validated a procedure for the determination of indicator congeners (ICs) of polychlorinated biphenyls (PCBs) (IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) in...     

The routine analysis of some specific isomers of polychlorinated biphenyl congeners in human milk

A mixture of 14 polychlorinated biphenyl (PCB) isomers of various congeners, representing approximately 70% of all human milk PCBs reported in the literature, was made up to identify and approximate their residues in human milk. Individual isomer levels varied from 5 to 103 nanograms per gram of milkfat with the 2,2',4,4',5,5'-hexachlorobiphenyl isomer as the major PCB contaminant of human milk. PCB isomer numbers 74, 118, 153, 138 and 180 made up approximately 75% of all PCBs as measured by this mixture. There was close agreement of total PCB isomer content in breast milk between electron capture gas chromatography and gas chromatographic mass spectrometry determinations. A major interference was encountered however for PCB isomer no. 52, whose residue level in the breast milk was approximately 3 X higher by gas liquid chromatography than by mass spectrometry.