Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Aroclor misidentification in environmental samples: how do we communicate more effectively between the laboratory and the data user?

Disposal of carbonless copy paper (CCP) paper sludge during the 1960s contaminated a site in the USA with PCBs. Despite historic records of CCP sludge disposal and absence of evidence of any other disposal, a dispute arose among the parties over the source of the PCBs. Aroclor 1242 is well documented as the PCB mixture used in CCP, yet Aroclors 1242, 1248, 1254, and 1260 were reported by the analytical laboratory. How could the PCBs at a single, small site be reported as four different Aroclors? Some claimed that there had to be at least four Aroclors source inputs to the site. Disposal of four different Aroclors at this site would simply defy logic and the historic record. Weathering of the mixtures is part of the story. A larger issue is the conflict between the intent of the USEPA 8082 method to determine the total PCB content in environmental samples to facilitate environmental cleanup and disposal decisions within a regulatory context versus the data users’ intent to identify the PCB sources. This inappropriate extension of the data leads to erroneous conclusions. To mitigate problems like this, laboratory analysis requests need to be matched to the intended data usage; conversely, the data must not be over-interpreted beyond the limits of the method. The PCB analysis community needs to develop a better articulation of the limits of Aroclor identification for the broader community that may naïvely assume that if the laboratory reports “Aroclor 1248,” then someone must have placed Aroclor 1248 at the site. After all, when a laboratory reports “lead” or “chloroform,” those identifications are never in question.     

Detailed PCB congener patterns in incinerator flue gas and commercial PCB formulations (Kanechlor)

In this study, we determined the detailed PCB congener patterns in flue gases from eight incinerators and four commercial PCB formulations (Kanechlors). About 160 PCB peaks were identified in samples using a DB-5 column and HRGC/HRMS. The concentration of incinerator stack emission gas ranged from 0.02 to 44 ngWHO-TEQ/Nm3. The ratios of dioxin-like PCBs in the total PCB concentration were from 3.4% to 25.7% and from 0.63% to 9.1% in stack emission gases and Kanechlor samples, respectively. The PCB congener profiles of Kanechlor samples were similar to those of previous studies. To determine characteristic congeners in flue gas and Kanechlor samples, principal component analysis (PCA) of the data was conducted using STATISTICA for Windows 5.0J (StatSoft, Inc.). As a result, we obtained four principal components (PCs) and accounted for 74% of the total variance. PC 1 was interpreted combustion, PC 2 and PC 3 were interpreted the difference in the number of substituted chlorines and, PC 4 could not be determined. Moreover, we obtained three groups according to the PCB congeners pattern among samples by PCA. These specific congeners that represent characteristics of each class were identified. These data will be useful for the source analysis of PCBs in the environment.     

Atmospheric PCB congeners across Chicago

We have measured PCBs in 184 air samples collected at 37 sites in the city of Chicago using an innovative system of high-volume air samplers mounted on two health clinic vans. Here we describe results of sampling conducted from November 2006 to November 2007. The samples were analyzed for all 209 PCB congeners using a gas chromatograph with tandem mass spectrometry (GC-MS/MS). The ΣPCBs (sum of 169 peaks) in Chicago ranged from 75 pg m(-3) to 5500 pg m(-3) and primarily varied as a function of temperature. The congener patterns are surprisingly similar throughout the city even though the temperature-corrected concentrations vary by more than an order of magnitude. The average profile resembles a mixture of Aroclor 1242 and Aroclor 1254, and includes many congeners that have been identified as being aryl hydrocarbon receptor (AhR) agonists (dioxin-like) and/or neurotoxins. The toxic equivalence (TEQ) and neurotoxic equivalence (NEQ) in air were calculated and investigated for their spatial distribution throughout the urban-industrial complex of Chicago. The NEQ concentrations are linearly correlated with ΣPCBs while the TEQ concentrations are not predictable. The findings of this study suggest that airborne PCBs in Chicago are widely present and elevated in residential communities; there are multiple sources rather than one or a few locations of very high emissions; the emission includes congeners associated with dioxin-like and neurotoxic effects and congeners associated with unidentified sources.     

Comparative aryl hydrocarbon hydroxylase induction activities of commercial PCBs in Wistar rats and rat hepatoma H-4-II E cells in culture

The activities of several commercial PCB mixtures as inducers of microsomal aryl hydroarbon hydroxylase (AHH) and ethoxyresorufin 0-deethylase (EROD) in male Wistar rats and rat hepatoma cells were dependent on the chlorine content (and congener distribution) of the mixtures. The was a correlation between the $\text{in vivo}$ and $\text{in vitro}$ induction potencies of these mixtures; the most active mixtures, Aroclors 1242, 1248 and 1254 contained 42–54% by weight of Cl whereas formulations with higher or lower (Aroclors 1221 and 1268 respectively) chlorine content exhibited lower activities. This corresponds with studies reported for PCB isomers and congeners in which the most active compounds are tetra-hexachlorobiphenyls.     

Distribution patterns of nitrobenzenes and polychlorinated biphenyls in water, suspended particulate matter and sediment from mid- and down-stream of the Yellow River (China)

Samples of water, suspended particulate matter (SPM) and sediment were collected from mid- and down-stream of the Yellow River. The distribution and concentration of 10 nitroaromatic compounds and polychlorinated biphenyls (PCBs) were extensively studied. The total concentration of 10 nitrobenzenes (SigmaNBs) varied from 0.269 to 9.052 microg l(-1) in water, from 2.916 to 164.4 microg kg(-1) dry weight in SPM, and from 0.954 to 14.72 microg kg(-1) dry weight in sediment. PCBs associated with the sediments, measured as the summed responses of Aroclor 1242, 1248, 1254, 1260 (in comparison to those of a standard 1:1:1:1 mixture), were found to be in the range of non-detectable to 5.98 microg kg(-1). In the samples collected, various PCB congeners showed similar distribution characteristics with congeners containing 3-5 chlorine atoms accounting for more than 96.4% of total PCB. In most of the samples, PCB concentrations occurred in the order: TetraCB > TriCB > PentaCB. Levels of SigmaNBs in the Yellow River were relatively low in comparison with values reported from other river and marine systems, and PCB levels were comparatively low. Relative to the PCBs, SigmaNBs showed significantly more difference among the various stations, presumably due to the influence of different pollution sources. No obvious correlation was observed between the pollutant concentrations and either the TOC or the grain size of the sediments.     

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk from the Pacific Northwest

Breast milk samples from 40 first-time mothers from the Pacific Northwest of the US and Canada were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Total PBDEs (summation operator PBDEs), calculated by summing values for the 12 PBDEs congeners analyzed, ranged from 6 to 321 ppb (lipid weight) (mean=96 ppb; median=50 ppb). In approximately 40% of the women (15/40), summation operator PBDEs>100 ppb lw in their milk, and four samples had levels >250 ppb lw. PBDE 47 was the dominant congener in most samples, whereas PBDE 153 was predominant in a few (3/40). summation operator PCBs were calculated by summing values for the 82 PCB congeners analyzed, and ranged from 49 to 415 ppb (lipid weight) (mean=147 ppb; median=126 ppb). approximately 30% of the mothers (13/40) have summation operator PBDEs> summation operator PCBs in their milk samples, and approximately 65% (25/40) have BDE 47>PCB 153 in breast milk samples, with BDE 47 averaging 3-fold greater levels than PCB 153. Clearly, the lower brominated PBDEs are surpassing PCBs as a major environmental concern in North America, and are likely affecting significant portions of the populations in these regions. PBDEs have become a major persistent organic pollutant. However, there are no positive correlations between levels of summation operator PBDEs and summation operator PCBs, or between levels of PBDE 47 and PCB 153, suggesting there may be some differences in exposure pathways for PBDEs and PCBs in humans.     

Development of a new polyclonal antibody for the determination of polychlorinated biphenyls in indoor air by ic-ELISA

A new polyclonal antibody (pAb) was prepared and used for the determination of polychlorinated biphenyls (PCBs) in air samples to promote the application of immunoassay technology in the determination of PCBs. Three PCB congeners immunogen mixture was used to stimulate immune responses in rabbits. The specific pAb to PCBs was obtained and used to develop an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA). A standard curve for Aroclor 1248 was prepared using concentrations ranging from 0.1 to 100 μg L^?1. The average IC₅₀ value was 16.21 μg L^?1 and the limit of detection at 10 % inhibition (IC₉₀) was 0.069 μg L^?1. The entire procedure was then evaluated using spiked air samples. The recoveries of Aroclor 1248 at various spiking levels in the air samples ranged from 84 to 113 %, with relative standard deviations of 3 to 6 %. Under optimum conditions, the cross-reactivity profiles of the assays were obtained using three selected congeners, four Aroclor products, and other structurally related compounds of PCBs. The assays were found to be highly specific for PCB congeners and Aroclors 1248 and 1242. The air samples were then analyzed using gas chromatography coupled with high-resolution mass spectrometry to confirm the ic-ELISA results. The attained results demonstrated that the proposed method was an effective and inexpensive technique for the PCBs determination in air samples.     

Polychlorinated biphenyls contamination in urban soil of Shanghai: level, compositional profiles and source identification

Surface soil samples taken from 55 sampling sites at the urban areas of Shanghai were collected and analyzed for the occurrence of 144 polychlorinated biphenyls (PCBs) by GC-μECD. The results showed that totally 74 PCB congeners were identified and the mean concentration of total PCBs was 3057 ng kg⁻¹ with a range of 232 to 11325 ng kg⁻¹. Compared with the related reports, the level of PCBs contamination in this study was approximately equal to the global background value in soils, but higher than Chinese background for rural and urban soils. According to the compositional profiles of PCBs homologues, a higher proportion of low chlorinated (from tri-CBs to hexa-CBs) was observed. The results indicated that PCB15 + 13, PCB18, PCB28, PCB104 + 47 and PCB153 were the most dominant congeners among the identified PCBs. Through homologues analysis, cluster analysis and principal component analysis (PCA), it was found that PCBs were stretched from mixed local sources, and appeared to be mostly originated by Aroclor 1260- and 1254-like mixtures as well as some samples influenced by Aroclor 1232 and 1242. The correlation analysis showed the relatively good correlation among the PCB homologues and soil total organic carbon (TOC), suggesting important influence of soil TOC on PCBs contamination in soil matrix in Shanghai region. The toxic equivalency (TEQ) concentrations of these six dioxin-like PCBs detected in urban soil samples range from 2.71 to 24.9 pg kg⁻¹-PCDDeq with a mean 8.18 pg kg⁻¹-PCDDeq.     

Characterization and risk assessment of polychlorinated biphenyls in soils and vegetations near an electronic waste recycling site, South China

This study aimed at identifying the levels of PCBs generated from e-waste recycling, and their potential impacts on the soils and vegetations as well. The ΣPCBs concentrations in soil and plant samples ranged from 7.4 to 4000 ng g(-1) and from 6.7 to 1500 ng g(-1), respectively. For the plant samples, Chrysanthemum coronarium L. from vegetable field and the wild plant Bidens pilosa L. from the burning site showed relatively higher PCB concentrations than other species. For the soil samples, the e-waste burning site had relatively higher PCB concentrations than the adjacent areas, and vegetable soils had higher PCB concentrations than paddy soils. The PCB concentrations showed a clear decreasing trend with the increasing distance from the e-waste recycling site. PCB 28, 99, 101, 138, 153, and 180 were the predominant congeners. Principal component analysis results showed a potential fractionation of PCB compositions from the burning site to the surroundings. The PCB congener pattern at the burning site was similar to Arochlor 1260, pointing to an input of non-domestic e-waste. Similar PCB congeners were found in soils and related vegetables, indicating they derived from the same source. The consumption of vegetables grown in soils near e-waste recycling sites should be strictly avoided due to the high PCBs in the plant tissues.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.     

Distribution characteristics of polychlorinated biphenyls in crucian carp (Carassius auratus) from major rivers in Korea

Polychlorinated biphenyls (PCBs) levels in crucian carp were determined at 20 locations along four major river systems, several small-scale rivers and a wetland in Korea. Twenty-eight congeners, ranging from tri- to hepta-CBs were detected. A gas chromatograph with a mass selective detector was used to quantify the individual PCB congeners. The objectives of this study were to investigate the levels of contamination of PCBs in freshwater fish and to observe the pattern of their distribution. The sampling locations were chosen among 31 sampling sites that are currently used as environmental residue checkpoints by the Korean Ministry of Environment. Concentrations of individual congeners ranged from not detectable (n.d.) to 0.75 ng g(-1) on a wet weight basis. The total concentrations of PCBs at each site ranged from n.d. to 5.41 ng g(-1) of wet weight. The most heavily contaminated site was the Nakdong estuary located near the Shinpyung-Janglim factory district. The PCB 153 and 138 were the principal congeners and penta- and hexa-chlorinated biphenyls comprised the main congener groups.     

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.     

Extensive biodegradation of polychlorinated biphenyls in Aroclor 1242 and electrical transformer fluid (Askarel) by natural strains of microorganisms indigenous to contaminated African systems

Evidence for substantial aerobic degradation of Aroclor 1242 and Askarel fluid by newly characterized bacterial strains belonging to the Enterobacter, Ralstonia and Pseudomonas genera is presented. The organisms exhibited degradative activity in terms of total PCB/Askarel degradation, degradation of individual congeners and diversity of congeners attacked. Maximal degradation by the various isolates of Askarel ranged from 69% to 86% whereas, Aroclor 1242, with the exception of Ralstonia sp. SA-4 (9.7%), was degraded by 37% to 91%. PCB analysis showed that at least 45 of the representative congeners in Aroclor 1242 were extensively transformed by benzoate-grown cells without the need for biphenyl as an inducer of the upper degradation pathway. In incubations with Aroclor 1242, no clear correlation was observed between percentage of congener transformed and the degree of chlorination, regardless of the presence or absence of biphenyl. Recovery of significant but nonstoichiometric amounts of chloride from the culture media showed partial dechlorination of congeners and suggested production of partial degradation products. Addition of biphenyl evidently enhanced dechlorination of the mixture by some isolates. With the exception of Ralstonia sp. SA-5, chloride released ranged from 24% to 60% in the presence of biphenyl versus 0.35% to 15% without biphenyl.     

Polychlorinated biphenyl congener patterns in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed, western Massachusetts, USA, using a novel statistical approach

A novel application of a commonly used statistical approach was used to examine differences in polychlorinated biphenyl (PCB) congener patterns among locations and sample matrices in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed in western Massachusetts, USA. The most prevalent PCB congeners in tree swallow tissue samples from the Housatonic River watershed were Ballsmitter Zell numbers 153, 138, 180, 187, 149, 101, and 170. These congeners were seven of the eight most prevalent congeners in Aroclor 1260, the PCB mixture that was the primary source of contamination in the Housatonic River system. Using paired-Euclidean distances and tolerance limits, it was demonstrated that congener patterns in swallow tissues from sites on the main stem of the Housatonic River were more similar to one another than to two sites upstream of the contamination or from a nearby reference area. The congener patterns also differed between the reference area and the two upstream tributaries and between the two tributaries. These pattern differences were the same in both pipper (eggs or just hatched nestlings) and 12-day-old nestling samples. Lower-chlorinated congeners appeared to be metabolized in nestlings and pippers compared to diet, and metabolized more in pippers compared to nestlings. Euclidean distances and tolerance limits provide a simple and statistically valid method to compare PCB congener patterns among groups.     

Organochlorine compounds (PCBs, PCDDs and PCDFs) in seafish and seafood from the Spanish Atlantic Southwest Coast

Concentrations and congener specific profiles of PCDD/Fs and PCBs were determined in edible fish and seafood species from the Coast of Huelva, in the Spanish southwest Atlantic coast. Five fish species, namely wegde sole (Dicologoglossa cuneata), common sole (Solea vulgaris), white seabream (Diplodus sargus), sardine (Sardina pilchardus), angler fish (Lophius piscatorius), two shellfish species (Donax trunculus and Chamelea gallina), common cuttlefish (Sepia officinalis) and prawns (Parapenaeus longirostris), frequently found and consumed in the area were analysed. Concentrations ranged from 861 to 23787pg/g wet weight for total PCBs, while 2,3,7,8-PCDD/Fs showed concentrations ranging from 0.2 to 1.18pg/g wet weight. WHO-TEQ concentrations ranged from 0.038 to 0.186pg WHO-TEQ(PCDD/Fs)/g wet weight, values well below the maximum concentrations established by the EU. When non- and mono-ortho PCBs were included the values increased to a maximum of 0.99pg WHO-TEQ(PCDD/Fs+PCBs)/g wet weight. The PCB and PCDD/F accumulation pattern found in the samples analysed showed a distribution typically reported for marine samples, and no remarkable differences were found between species. The PCBs were the ones contributing with the highest percentage to the total TEQ content in most species studied. Concerning the seafood, specially prawns and shellfish, the opposite was observed and PCDD/Fs were found to contribute with a higher percentage than PCBs. The congener specific contribution to the TEQ showed PCB 126 followed by 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF as the most abundant ones.     

Compound-specific isotopic and congener-specific analyses of polychlorinated biphenyl in the heat medium and rice oil of the Yusho incident

Compound-specific isotope analysis (CSIA) can be used to examine the source and transformation processes of organic pollutants in the environment. We performed a carbon stable isotope analysis of polychlorinated biphenyl (PCB) congeners in the PCB heat-transfer medium (heat medium) and the original Kanechlor-400 (KC-400, a commercial brand of PCBs) involved in the Yusho incident. The main purpose is to investigate whether isotope fractionation occurred in the rice oil deodorization process that caused the incident. The carbon isotope ratios (δ¹³C values) of the targeted PCB congeners ranged from ? 29.39 to ? 27.00‰ in the heat medium and from ? 28.77 to ? 27.05‰ in the original KC-400. No significant differences were found in the δ¹³C values, suggesting carbon isotope fractionation did not occur for the targeted PCB congeners in the heat medium when deodorization of rice oil occurred at temperatures above 200 °C. Furthermore, we also conducted a congener-specific analysis of 64 PCB congeners found in the heat medium and rice oil contaminated by it. The total PCB congener concentrations were 503 mg/g in the heat medium and 81 μg/g in the rice oil. The concentrations of the highly chlorinated congeners were significantly lower in the heat medium than in the original KC-400, and the compositional ratios of the lowly chlorinated congeners were relatively lower in the rice oil than in the heat medium. These results suggest that the PCB congener patterns gradually changed from that of the original KC-400 in the deodorization process and subsequent contamination into the rice oil. Thus, a combination of CSIA and congener-specific analysis is a new approach for investigating the changing PCB congener profiles in samples from the Yusho incident.     

Polychlorinated biphenyls in small mammals from contaminated landfill sites

PCBs in small mammals living in a contaminated landfill site varied in both concentration and congener composition, reflecting both the feeding strategy of each species and the chlorination of the congeners. Body concentrations of SigmaPCB on a 1:1:1 Arochlor (1242:1254:1260) basis gave a rank order of Sorex araneus > Apodemus sylvaticus > Microtus agrestis. Comparisons with data for other PCB-contaminated sites suggest that the SigmaPCB values in S. araneus from the landfill site may be of sufficient magnitude to inhibit reproductive capability and to cause other major organ dysfunction. There were also inter-specific differences in the whole body concentrations of the individually quantified congeners. For S. araneus, the rank order of concentrations of the selected ICES 7 marker PCB congeners was: No. 153>138>180>118>28>101>52. In M. agrestis the rank order was: No. 28>118>153>138>180, 52>101. The congener order for A. sylvaticus differed from both S. araneus and M. agrestis, but was more similar to the latter, being: No. 153>138>118>180>28>52, 101. The contribution of the different congeners to SigmaPCB in the mammals reflects the degree of chlorination of different congeners but varies with feeding strategy of the species. In the insectivorous S. araneus, heavily chlorinated congeners (Nos 153, 138 and 180) are most abundant, whereas the herbivore, M. agrestis showed congeners Nos 28 and 118 to be present in the highest amounts, whilst the equivalent pattern for the more omnivorous A. sylvaticus was intermediate between S. araneus and M. agrestis. The high concentrations of PCBs in S. araneus relative to the other species, suggests that it may serve as a useful biomarker of terrestrial environmental pollution by organochlorines.     

PCBQ: Computerized quantification of total PCB and congeners in environmental samples

Computerized methodologies for the quantification of total PCBs, PCB in Aroclor mixtures and individual PCB congeners in environmental samples are presented. The method for total PCBs is based on a multiple-linear regression analysis using data from capillary gas chromatography of Arocolor standards. PCB congeners were identified and their weight percentages determined in Aroclor mixtures by GC/MS. PCB congeners and total PCBs were accurately quantified in predetermined test data and environmental samples.