Determination of 26 polychlorinated biphenyls congeners in soil samples using microwave-assisted extraction with open vessel and gas chromatography

A procedure focused on microwave-assisted extraction in open vessel (MAE-OV) and gas chromatography with electron capture detection (GC-ECD) was used for the determination of 26 congeners of polychlorinated biphenyls (PCBs) in soil samples. The limit of detection (LOD) and limit of quantification (LOQ) were evaluated for commercial PCBs mixture Aroclor1260. LOD and LOQ were calculated for each PCB congener, in the ranges (0.03–0.27?ng?g^?1) and (0.11–0.70?ng?g^?1), respectively. After optimization, 26 PCBs congeners were successfully extracted from soil samples with recovery amounts ranging between 84.7% and 117.3% for all PCBs congeners. The evaluated method of MAE-OV showed good separation and extraction of all PCBs congeners from soil samples. Extraction parameters such as solvent choice, power and extraction time were investigated. This study indicated that MAE-OV could be an interesting alternative method to extract PCBs from soils, since it is economical, easy, fast and requires low amounts of solvents.     

Occurrence of organochlorine pesticides and polychlorinated biphenyls in soils and sediments from Eastern Romania

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), such as DDT and analogues, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB), were measured in surface soils and sediments from Eastern Romania. Thirty-nine soil samples from the forested zone, eight soil samples from a municipal waste-disposal site, and 10 sediment samples from the Bahlui River along the Iassy city were analysed using accelerated solvent extraction (ASE) and gas chromatography coupled to electron capture detection or mass spectrometry. The low mean concentrations of OCPs (11–31 and 22–84?ng?g^?1 for HCHs and DDTs, respectively) and PCBs (8–43?ng?g^?1) in soil samples from the forested zone suggest that contamination at most of these sites occurred predominantly through atmospheric transport from zones where these compounds were used and subsequently through atmospheric deposition. Contrarily, soil samples collected in the vicinity of a waste-disposal site near Iassy contained higher mean levels of PCBs (278?ng?g^?1, range 34–1132?ng?g^?1) than OCPs (6 and 101?ng?g^?1 of soil for HCHs and DDTs, respectively). The sediment samples collected along the Bahlui river throughout the Iassy city revealed higher mean levels of PCBs (59?ng?g^?1, range 24–158?ng?g^?1) compared with OCP levels (2 and 37?ng?g^?1 of soil for HCHs and DDTs, respectively). Furthermore, PCB profiles and concentrations in the sediment samples varied considerably along the river due to a wide variety of sources, such as different industries and waste sites. Although their sources are difficult to evaluate, the presence of POPs at most sites (especially at the waste-disposal site) may constitute a potential health hazard.     

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.     

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.     

Polychlorinated naphthalene concentrations and profiles in cheese and butter,and comparisons with polychlorinated dibenzo-p-dioxin,polychlorinated dibenzofuran and polychlorinated biphenyl concentrations

Polychlorinated naphthalenes (PCNs) are candidates for inclusion in the Stockholm Convention on persistent organic pollutants. PCNs are structurally and toxicologically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and its analogues. Intake in food is considered to be an important human exposure pathway for PCNs. In this preliminary study, cheese and butter samples were analysed for PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) using an isotope dilution gas chromatography high-resolution mass spectrometry method. The aim of this study was to evaluate the PCN concentrations in the cheese and butter samples and to compare them with the PCDD, PCDF and PCB concentrations. The PCN concentrations were 5.6–103 pg g^?1 of wet weight in the seven cheese samples tested and 5.0–199 pg g^?1 of wet weight in the seven butter samples tested. The mass concentrations of lower chlorinated congeners were greater than those of the higher chlorinated congeners. Congeners of CN45/36, CN27/30 and CN33/34/37 were much more abundant than other congeners found in tetrachlorinated PCNs. Congeners of CN51, CN66/67 and CN73 were determined to be the predominant congeners in penta-, hexa- and heptachlorinated homologs, respectively. The PCNs contributed around 5% of the total PCN, PCDD, PCDF and PCB toxic equivalence (TEQ) values. CN73 was found to be the dominant PCN congener and contributed more than 40% to the PCN TEQ value. Congeners CN66/67, CN69 and CN63 were also found at relatively high levels. The PCB congener CB118 was the predominant congener (by mass-based concentration) of the 12 dioxin-like PCBs (dl-PCBs). The PCBs contributed 53.8% of the total TEQ, and congener CB126 contributed more than any other compound that was analysed to the total TEQ. The PCDDs and PCDFs contributed 11.6% and 29.7% of the total TEQ values, respectively.     

Direct analysis of polychlorinated biphenyls in heavily contaminated soils by thermal desorption/gas chromatography/mass spectrometry

A robust analytical method is presented for the direct determination of polychlorinated biphenyls in soil samples by thermal desorption/gas chromatography/mass spectrometry. The method is simple to perform (thermal desorption and analysis are performed in-line employing a limited amount of sample, 2?mg) and eliminates the need for any solvent and time-consuming extraction. The analytical procedure was optimized using a soil sample spiked with Aroclor 1254 and Aroclor 1260 and validated with a certified industrial soil sample for which the concentration of thirteen PCB congeners are known. Limits of detection were sensitive to matrix effects and varied substantially among analytes. The matrix effect resulted in a reduction of the limits of detection by 1.5–10 times. However, it was found that the matrix effect is not due to ion suppression but to the increase of the noise of selected ion monitoring (SIM) traces, indicating that no limitation exists with using a single surrogate standard. By employing a 13C-labelled PCB internal standard, limits of detection in the range of 0.8 to 10?µg?g^?1 of soil were obtained. The obtained experimental results demonstrated that the proposed analytical method can be conveniently applied for screening a large number of heavily contaminated soil samples thus avoiding the employment of harmful solvents and time-consuming extraction procedures.     

Levels of polycyclic aromatic hydrocarbons,polychlorinated byphenyls,methylmercury and butyltins in the natural UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay,Spain)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), methylmercury (MeHg⁺) and butyltins (mono-, di- and tri-butyltin, MBT, DBT and TBT) were monitored in oysters (Crassostrea sp.) and sediments collected in different sampling points of the UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay) from March 2006 to June 2007. In the case of oyster samples, concentrations in the 290–1814 µg kg^?1 (PAHs), 70–475 µg kg^?1 (PCBs), 75–644 µg kg^?1 (MeHg⁺) and 200–1300 µg kg^?1 (as a sum of the three butyltins) ranges were obtained. In most samples TBT was the most abundant butyltin, followed by DBT and MBT. It should be highlighted that most samples exceeded the highest range (367 µg kg^?1) found in the last mussel watch programme carried out by the National Oceanic and Atmospheric Administration (NOAA) for butyltins in oyster samples. This could be due to the presence of a shipyard in the estuary. Sediment concentrations ranged as follows: total PAHs (856–3495 µg kg^?1) and total PCBs (58–220 µg kg^?1). Organometallic species were always below the limits of detection (LODs) (0.24 µg kg^?1 for MeHg⁺, 0.6 µg kg^?1 for MBT, 0.48 µg kg^?1 for DBT and 1.1 µg kg^?1 for TBT). In both sediment and oyster PAH sources were mostly combustion. In the case of PCBs, 4-6 chlorine-atom congeners were the most abundant ones. Slight differences in the profile of PAHs as well as PCBs can be detected when the matrices were compared with each other. Finally, in the case of PAHs, sediment and water column played the main role in the accumulation pathway into the organisms in all the sampling stations.     

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%.     

The use of solid-phase microextraction to rapidly measure dissolved PCBs in natural waters

A method to measure dissolved polychlorinated biphenyls (PCBs) in natural waters on 30?min time frames using negligible depletion non-equilibrium solid-phase microextraction (SPME) was developed with detection limits ranging from 0.6 to 5.2?ng?L^?1. SPME fibres made from optical cable were inserted into a glass tube and attached to the shaft of a motor that revolved at 130?rpm to move the SPME fibres through the sampled water at a constant rate. To test for matrix interferences, measurements were made in three solutions with the same known dissolved PCB concentration but different matrices. Dissolved PCB measurements made in the presence of 8?mg?L^?1 of DOC and 200?mg?L^?1 of suspended solids were not significantly different from measurements made in deionized water, demonstrating that neither matrix interfered with SPME measurements of dissolved PCBs. PCB concentrations measured by XAD-2 resin extraction were greater than SPME measurements, suggesting that XAD measurements included DOC-associated PCBs.     

Dechlorination of polychlorinated biphenyls in electron impact mass spectrometry: Regioselective analysis using 35Ci-labelled compounds

Four tetrachlorinated bipbenyls were chlorinated with ³⁵Cl₂ to yield seventeen polychlorinated biphenyls (PCBs) substituted once or twice with chlorine enriched in ₃₅Cl. Gas chromatographic analysis of the mixtures allowed the identification of the labelled PCBs produced by comparison of their relative retention times with published values. This also permitted the assignment of the position of the labels in these molecules. Mass spectrometric determination of the ³⁵Cl/³⁵Cl ratio of the ions corresponding to successive dechlorination of these PCBs in positive-ion electron impact (EI) allowed quantification of the residual ³⁵Cl label in these ions. Chlorines in the ortho position are lost preferentially to those in meta or para positions. The first dechlorination reaction was found to be totally regioselective for at least two PCB congeners.     

PAH and PCB determination of the concentration gradient in moss Pleurozium schreberi near a highway,and seasonal variability at the background reference site

Moss (Pleurozium schreberi) was investigated as biomonitor of atmospheric polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Samples were collected at a distance of 10, 50 and 100 m from a highway and were seasonally collected in a forest stand near a regional background air pollution station situated approximately 30 km from the highway. The samples from the background area were dried using two different techniques in parallel, air-drying and freeze-drying. Simultaneous pressurised liquid extraction of PAHs and PCBs was performed, followed by purification using gel permeation chromatography of the crude extract. The concentration of the 15 most important Environmental Protection Agency (EPA) PAHs was determined by gas chromatography coupled with ion-trap mass spectrometry with a selected ion storage acquisition programme, and the PCB concentrations were determined using a mass spectrometer operated in tandem mass spectrometry (MS/MS) mode. Acceptable recoveries and quality parameters for PAHs and PCBs were achieved with the use of pressurised liquid extraction followed by gel permeation chromatography. The detection limit was <0.76 ng g^?1 for PAHs and <0.04 ng g^?1 for PCBs. Possible contamination of the moss samples by 3-ring PAHs and PCBs in the atmosphere was found during air drying. Increased PAH and PCB concentrations caused by car engine exhausts and by asphalt and oil evaporation were found near the highway. Generally, the PAH and PCB concentrations in moss decreased exponentially with distance from the highway. The organic compound concentrations close to the background station showed seasonal fluctuations corresponding to the fluctuations in the local air temperature and particle concentration.     

Effect of six triorganotin(IV) compounds on nitrification and ammonification in soil

The effects of six triorganotin(IV) compounds and of Thiram on nitrification and ammonification in soil were investigated. Low concentrations of up to 50 μg g^?1 of the triorganotin(IV) compounds enhanced nitrate-nitrogen (NO₃^?-N) production in soil. Except for diphenylbutyltin bromide, which inhibited nitrification at 250 μg g^?1, the other triorganotin(IV) compounds were inhibitory at concentrations of 100 μg g^?1 to less than 250 μg g^?1. At 10 μg g^?1, only triphenyltin acetate was less inhibitory towards nitrification compared with Thiram. At 250 μg g^?1, Thiram exerted a strongly persistent inhibitory effect towards nitrification. The NO₃^?-N level recorded 28 days after application was only 0.10 μg g^?1 soil. With the triorganotin compounds NO₃^?-N levels of 7.05–12.06 μg g^?1 soil were recorded 28 days following their application. The deleterious effects of the triorganotin(IV) compounds were less persistent and recovery of nitrification was evident seven days after application. Low concentrations of Thiram and triorganotin(IV) compounds inhibited ammonification, whereas higher concentrations enhanced ammonification. Complete inhibition of ammonification was attained 21–28 days after application of Thiram at 50 μg g^?1. On the other hand, with the triorganotin(IV) compounds, except for diphenylbutyltin bromide at 10–50 μg g^?1, ammonification persisted at all concentrations 28 days after application.     

Quantitative analysis of selected PCB congeners in marine matrix reference materials using a novel cyanobiphenyl stationary phase

A novel p,p-cyanobiphenyl stationary phase (p-cyanobiphenyl, p-allyloxy methylpolysiloxane) has been evaluated for the GC investigation of polychlorinated biphenyls (PCBs). Several PCB congeners which coelute on the phases typically used for PCB analysis (e.g. 5% phenyl methylpolysiloxane) are separated on the p,p-cyanobiphenyl phase, including the hexachlorobiphenyl congeners PCB 163, PCB 164, and PCB 138. In this work, a p,p-cyanobiphenyl stationary phase was used to measure selected PCB congeners in two Standard Reference Materials (SRMs) available from the National Institute of Standards and Technology (NIST), and two Certified Reference Materials (CRMs) available from the Community Bureau of Reference (BCR). The materials analyzed were SRM 1588, Organics in Cod Liver Oil; SRM 1945, Organics in Whale Blubber; CRM 349, Chlorobiphenyls in Cod Liver Oil; and CRM 350, Chlorobiphenyls in Mackerel Oil. Concentrations are reported for several PCB congeners which coelute on the 5% phenyl methylpolysiloxane, including PCB 163 and PCB 164.     

Use of a polar ionic liquid as second column for the comprehensive two-dimensional GC separation of PCBs

The orthogonality of three columns coupled in two series was studied for the congener specific comprehensive two-dimensional GC separation of polychlorinated biphenyls (PCBs). A non-polar capillary column coated with poly(5%-phenyl–95%-methyl)siloxane was used as the first (¹D) column in both series. A polar capillary column coated with 70% cyanopropyl-polysilphenylene-siloxane or a capillary column coated with the ionic liquid 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethane-sulfonyl)imide were used as the second (²D) columns. Nine multi-congener standard PCB solutions containing subsets of all native 209 PCBs, a mixture of 209 PCBs as well as Aroclor 1242 and 1260 formulations were used to study the orthogonality of both column series. Retention times of the corresponding PCB congeners on ¹D and ²D columns were used to construct retention time dependences (apex plots) for assessing orthogonality of both columns coupled in series. For a visual assessment of the peak density of PCBs congeners on a retention plane, 2D images were compared. The degree of orthogonality of both column series was, along the visual assessment of distribution of PCBs on the retention plane, evaluated also by Pearson's correlation coefficient, which was found by correlation of retention times t_R,i,2D and t_R,i,1D of corresponding PCB congeners on both column series. It was demonstrated that the apolar + ionic liquid column series is almost orthogonal both for the 2D separation of PCBs present in Aroclor 1242 and 1260 formulations as well as for the separation of all of 209 PCBs. All toxic, dioxin-like PCBs, with the exception of PCB 118 that overlaps with PCB 106, were resolved by the apolar/ionic liquid series while on the apolar/polar column series three toxic PCBs overlapped (105 + 127, 81 + 148 and 118 + 106).     

Real-time immuno-PCR assay for detecting PCBs in soil samples

A fast and robust assay, based on immuno-polymerase chain reaction (IPCR) techniques, was developed for the detection of polychlorinated biphenyls (PCBs) in soil samples. Real-time IPCR (rt-IPCR) is a powerful technique that combines enzyme-linked immunosorbent assay (ELISA) with the specificity and sensitivity of PCR. In our assay, indirect ELISAs based on immobilization of PCB37 hapten–ovalbumin conjugates was used for evaluation of the immune response. The effect of optimal reagent concentrations to reduce background fluorescence was also investigated. Using the optimized assay, the linear sensitivity range of the assay covered more than six orders of magnitude, and the minimum detection limits reached 5 fg ml^–1 antigen. Rt-IPCR was tested for its cross-reactivity profiles using four selected congeners and four Aroclor products. The assays were highly specific for congeners but less specific for Aroclor1242. We took four soil samples to validate the method, and the results were confirmed by gas chromatography/mass spectrometry (GC/MS). The rt-IPCR results for soil samples correlated well with the concentrations of PCBs obtained by GC/MS (r = 0.99, n = 6). These data indicate that this highly specific, sensitive, and robust assay can be modified for detecting PCB compounds in the environment.     

Analysis of polychlorinated biphenyls in transformer oils by automated on-line coupling reversed phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) Interface

An automated method for the direct analysis of polychlorinated biphenyls (PCBs) in transformer oil is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of reversed phase liquid chromatography and gas chromatography (RPLC-GC). In this fully automated system, the oil is injected directly with no sample pre-treatment step other than dilution with n-propanol and filtration. In the LC step, PCBs are separated from other components of the oils using methanol/water (90:10 v/v) as mobile phase, at a flow rate of 1?mL?min^?1. The LC fraction containing the PCBs is automatically transferred to the GC by the TOTAD interface and GC analysis enables the separation of the PCB congeners. The proposed method is compared with two other methods: the European Norm (UNE-EN-61619) and that of the American Society for Testing and Materials (ASTM) (D4059-00). The proposed method practically eliminates the time-consuming sample preparation step and avoids errors caused by sample manipulation. The total PCB concentrations obtained with the three methods are similar.     

Sensitive GC/MS determination of 15 isomers of chlorobenzoic acids in accelerated solvent extracts of soils historically contaminated with PCBs and validation of the entire method

Chlorobenzoic acids (CBAs) are the major metabolite of aerobic bacterial degradation of polychlorinated biphenyls (PCBs). A rapid and simple simultaneous derivatisation method has been developed for gas chromatography-mass spectrometry determination in historically PCB-contaminated soils for 15 isomers of mono-, di-, tri-, tetra-, and pentachlorobenzoic acids in CBA mixtures. Two derivatisation agents (diazomethane and methyl chloroformate) and various conditions were evaluated (temperature, time, solvents, catalysts) in terms of efficiency. The optimised derivatisation method with diazomethane and 1% methanol running 1 hour at 5°C was used for derivatisation of extracts of soils and river sediment from historically PCB-contaminated sites; the extracts were prepared using accelerated solvent extraction by a previously described method. Methylated CBAs were separated by gas chromatography using a system with two different common columns, DB-5 and DB-200, in series-coupled (tandem) arrangement and detected by EI-MS. A clean-up with a gel permeation chromatography was carried out to remove soil interfering matrix compounds as well as major portion of PCBs. The limits of quantification ranged between 1 and 10 ng g^?1 of individual CBA in the soil. The procedure was applied to various soil samples from Lhenice (Czech Republic) highly contaminated with PCBs. CBAs were found in all tested soils and also in the river sediment. The most contaminated soil contained all CBAs representatives under the study with a total concentration of 3.1 µg g^?1 of dry soil.     

Determination of polychlorinated biphenyls by liquid chromatography–atmospheric pressure photoionization–mass spectrometry

This study presents the atmospheric pressure photoionization (APPI) of high‐chlorinated (five or more chlorine atoms) polychlorinated biphenyls (PCBs) using toluene as dopant, after liquid chromatographic separation. Mass spectra of PCB 101, 118, 138, 153, 180, 199, 206 and 209 were recorded by using liquid chromatography‐APPI‐tandem mass spectrometry (LC‐APPI‐MS/MS) in negative ion full scan mode. Intense peaks appeared at m/z that correspond to [M ? Cl + O]^? ions, where M is the analyte molecule. Furthermore, a detailed strategy, which includes designs of experiments, for the development and optimization of LC‐APPI‐MS/MS methods is described. Following this strategy, a sensitive and accurate method with low instrumental limits of detection, ranging from 0.29 pg for PCB 209 to 8.3 pg for PCB 101 on column, was developed. For the separation of the analytes, a Waters XSELECT HSS T3 (100 mm × 2.1 mm, 2.5 µm) column was used with methanol/water as elution system. This method was applied for the determination of the above PCBs in water samples (surface water, tap water and treated wastewater). For the extraction of PCBs from water samples, a simple liquid–liquid extraction with dichloromethane was used. Method limits of quantification, ranged from 4.8 ng l^?1, for PCB 199, to 9.4 ng l^?1, for PCB 180, and the recoveries ranged from 73%, for PCB 101, to 96%, for PCB 199. The estimated analytical figures were appropriate for trace analysis of high‐chlorinated PCBs in real samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Problems in the Determination of Polychlorinated Biphenyls

The presence of aromatic hydrocarbons in pesticide-grade hexanes affects the elution patterns of polychlorinated biphenyls (PCB) and chlorinated hydrocarbon pesticides from silicic acid columns. Several batches of silicic acid Silicar® (Mallinckrodt) were contaminated with 0.031–0.163 mcg/g of PCB expressed as Aroclor® 1254. Chlorinated naphthalenes accompany PCB on silicic acid chromatography and their presence can be detected from an absorption maximum at 306 nm, A^1% _1cm = 329. PCB of the Aroclor® 1254 type were detected in American eel (Anguilla rostrata), herring (Clupea harengus), and Atlantic salmon (Salmo salar) in concentrations of 0.63–0.75, 0.32–0.54, and 0.45 mcg/g wet weight, respectively. Commercial fish oil contained 3.55 mcg/g of PCB.     

Relative performance of immunochemical (enzyme-linked immunosorbent assay) and gas chromatography-electron-capture detection techniques to quantify polychlorinated biphenyls in mussel tissues

Results from polychlorinated biphenyls (PCB) analyses of mussel tissue extracts by immunoassay (PCB RaPID Assay^®) and conventional gas chromatography-electron-capture detection (GC-ECD) are described and compared. Mussels from natural populations with diverse concentrations of PCBs, mussel tissue fortified with technical Aroclor^® 1254 and a certified reference material are included.A strong correlation is reported between “total” PCBs quantified by both techniques (r²=0.95, n=27). Immunoassay results, however, exhibited lower values compared to GC-ECD, particularly when GC results are corrected for procedural recovery. A reduced antibody response, due to differences in the congener composition between the mussel extracts and Aroclor^® 1254 (used to raise and calibrate the ELISA), provides the most likely explanation for this difference. Non-parametric statistical analyses confirmed that, although differing from Aroclor^® 1254, PCB congener compositions in the mussel extracts most closely resemble that of Aroclor^® 1254. At very high PCB concentrations (>30 μg g⁻¹ dry weight), however, ELISA results are statistically different (P<0.01) from GC-ECD results, which is likely to be related to the solvation capacity of ELISA diluent. Similarity analysis showed high correlations between the most prominent congeners in Aroclor^® 1254 and immunoassay results. This analysis did not, however, identify a specific chlorine substitution pattern to which the immunoassay preferentially responded.Whilst GC-ECD affords the capability to quantify individual congeners of different reactivity and toxicity, the data reported do indicate that immunoassay offers a rapid and inexpensive alternative method for estimation of “total” PCBs at environmentally significant levels. It is, however, necessary to remove extraneous lipids to reduce matrix effects in the immunoassay.