Concentrations Of Individual Congeners Research Articles

Understanding possible causes of exceeding dioxin levels in palm oil by-products: An explorative study

The Rapid Alert System for Food and Feed (period 1999–2014) reported exceeding levels of dioxins (polychlorinated dibenzo-p-dioxinsand dibenzofurans (PCDD/Fs)) in palm oil by-products, such as palm fatty acid distillate (PFAD) and hydrogenated palm fatty acid distillate (HPFAD), but not in crude and refined palm oil. The aim of the present study was to gain insight into the occurrence and congener profiles of dioxin contamination during industrial processing of crude palm oil into refined oil and its by-products PFAD and HPFAD via analysis of individual congener concentrations. In total, 1217 samples from an industrial process were collected at four different points, crude palm oil at delivery (N = 202), fresh bleaching earth before bleaching (N = 84), PFAD after deodorising palm oil (N = 553), and HPFAD after hydrogenation of PFAD (N = 378). Congener profiles were analysed by GC-HRMS, and toxic equivalent (TEQ) levels were calculated using toxic equivalence factors (TEF) of WHO2005 to assess non-compliance to legal limits. All dioxin levels in crude palm oil samples were far below the action limit. All dioxin levels in fresh bleaching earth were in compliance with the maximum level. For the by-product samples, such as PFAD, 0.6% exceeded the action level, but all were below the maximum level (ML). However, for 1.3% of the HPFAD samples, the TEQ level exceeded the ML.In-depth analysis of the congener profiles revealed that after the hydrogenation step, the concentration of the lower chlorinated congeners in the HPFAD samples was higher than in the PFAD samples. The hydrogen atoms possibly replaced the chlorine atoms during hydrogenation. As these lower chlorinated congeners have a higher TEF, when they are regulated, their contribution to the calculated TEQ is higher, which resulted in some HPFAD samples exceeding the legal limit. Further research is needed to obtain insight into the changes in PCDD/F congener profiles during the hydrogenation of palm oil products.

Association of Polybrominated Diphenyl Ethers (PBDEs) and Polychlorinated Biphenyls (PCBs) with Hyperthyroidism in Domestic Felines, Sentinels for Thyroid Hormone Disruption

BackgroundHyperthyroidism is the most common endocrine disorder observed in domestic felines; however, its etiology is largely unknown. Two classes of persistent organic pollutants, polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) are known to interfere with thyroid hormone (TH) signaling and regulation; thus, it is postulated that they contribute to the etiopathogenesis of feline hyperthyroidism and pose a risk to humans and other species. In this case-control study, the concentrations of 13 PBDE and 11 PCB congeners were measured by gas chromatography mass spectrometry in serum or plasma samples from 20 hyperthyroid and 31 control cats in order to investigate the association between concentration of PBDE and PCB congeners and feline hyperthyroidism. Logistic regression analysis was used to determine whether elevated concentrations of individual congeners were associated with a higher risk of feline hyperthyroidism.ResultsHyperthyroid cats had higher concentrations of four PBDE congeners (BDE17, BDE100, BDE47, and BDE49) and five PCB congeners (PCB131, PCB153, PCB174, PCB180, and PCB196), compared to control cats. In addition, the sum of both PBDE and PCB congener concentrations were elevated in the hyperthyroid group compared to control cats; however, only the increased PCB concentrations were statistically significant. The sum total PBDE concentrations in our feline samples were approximately 50 times greater than concentrations previously reported in human populations from a geographically similar area, whereas sum total PCB concentrations were comparable to those previously reported in humans.ConclusionsThese observational findings support the hypothesis that PBDEs and PCBs may contribute to the etiopathogenesis of hyperthyroidism in felines. As domestic house cats are often exposed to higher concentrations of PBDEs than humans, they may serve as sentinels for the risk of TH disruption that these pollutants pose to humans and other species.

Impacts of PCB analytical interpretation uncertainties on dechlorination assessment and remedial decisions

Laboratory analyses of polychlorinated biphenyls (PCBs) often do not quantitate the 209 individual PCB congeners, thereby requiring analyst interpretation to determine individual congener concentrations. Error introduced during this interpretation is subsequently propagated to calculated surrogate variables, such as the number of chlorines per biphenyl (CPB), and the molar dechlorination product ratio (MDPR), which are used to assess the extent of dechlorination and inform remedial decisions. The present work applies a Monte Carlo (MC) analysis to assess current methods for quantitating co-eluting congeners and the errors that could occur in individual congeners and derived CPB and MDPR estimates. Synthetic chromatograms, which were created using two alternative methods (random assignment and assignment based on relative proportions in Aroclors) for assigning mass to co-eluting congeners, were compared to their fully-quantitated counterparts. The percent error introduced in total PCB (∑PCB) concentration ranges from approximately −60% to +50%. Similarly, the errors associated with CPB and MDPR estimates range from approximately −20% to +20% and −120% to +30%, respectively. Uncertainties introduced during congener analysis and propagated to surrogate variables can thus be substantial, and should be considered in assessments of the extent of dechlorination and associated remedial decisions.

Spatio-temporal trends of PCBs in the Swedish freshwater environment 1981-2012.

Polychlorinated biphenyls (PCBs) have been monitored in perch (Perca fluviatilis), pike (Esox lucius), and Arctic char (Salvelinus alpinus) in reference lakes since the late 1960s. Temporal trends and spatial patterns are currently monitored in nine and 32 lakes, respectively. Overall, PCB concentrations are decreasing. However, this is not consistent for all congeners across all lakes and species. Perch has comparatively low PCB concentrations relative to suggested target levels, but individual congener concentrations in some lakes are concerningly high. No temporal trend is seen for CB-118 and CB-153 in perch, but significant decreasing trends exist for Arctic char and pike, for which monitoring started earlier than for perch. The lower/higher chlorinated congener ratio decreased over time in most lakes, indicating fewer new emissions. CB-118 and CB-153 concentrations in perch show spatial gradients across Sweden, with higher concentrations found near urban/industrial areas.

Monitoring organic and inorganic pollutants in juvenile live sea turtles: Results from a study of Chelonia mydas and Eretmochelys imbricata in Cape Verde

Despite the current environmental concern regarding the risk posed by contamination in marine ecosystems, the concentrations of pollutants in sea turtles have not been thoroughly elucidated. In the current study, we determined the concentrations of 18 organochlorine pesticides (OCPs), 18 polychlorinated biphenyls (PCBs), 16 polycyclic aromatic hydrocarbons (PAHs) and 11 inorganic elements (Cu, Mn, Pb, Zn, Cd, Ni, Cr, As, Al, Hg and Se) for the first time in two sea turtle species (Chelonia mydas and Eretmochelys imbricata). Only five of the 18 analyzed OCPs were detected in both species. The average total OCP concentration was higher in green turtles than in hawksbills (0.33ng/ml versus 0.20ng/ml). Higher concentrations of individual congeners and total PCBs were also detected in green turtles than in hawksbills (∑PCBs=0.73ng/ml versus 0.19ng/ml), and different PCB contamination profiles were observed in these two species. Concerning PAHs, we also observed a different contamination profile and higher levels of contamination in green turtles (∑PAHs=12.06ng/ml versus 2.95ng/ml). Di- and tri-cyclic PAHs were predominant in both populations, suggesting a petrogenic origin, rather than urban sources of PAHs. Additionally, all of the samples exhibited detectable levels of the 11 inorganic elements. In this case, we also observed relevant differences between both species. Thus, Zn was the most abundant inorganic element in hawksbills (an essential inorganic element), whereas Ni, a well-known toxicant, was the most abundant inorganic element in green turtles. The presence of contaminants is greater in green turtles relative to hawksbill turtles, suggesting a greater exposure to hazardous chemical contaminants for green turtles. These results provide baseline data for these species that can serve for future monitoring purposes outlined in the EU's Marine Strategy Framework Directive.

In-filter PCDF and PCDD formation at low temperature during MSWI combustion

This case study investigated PCDF and PCDD emissions from a 65MW waste-to-energy plant to identify why an air pollution control system remodeling to accommodate increased production resulted in increased TEQ concentrations. Pre- and post-filter gases were collected simultaneously in four sample sets with varying filter temperatures and with/without activated carbon injection. Samples were analyzed to determine total PCDF and PCDD concentrations, as well as homologue profiles, and concentrations of individual congeners (some remained co-eluted). The total post filter PCDD concentrations where found to increase while the concentrations of PCDF and 2,3,7,8-substituted congeners declined. An investigation of the individual congener concentrations revealed that the increase of PCDD concentrations were due to a few congeners, suggesting a single formation route. The study also concludes that vital information about the formation could be obtained by not restricting the analysis to just the 2,3,7,8-substituted congeners.

Serum concentrations of polybrominated diphenyl ethers (PBDEs) and a polybrominated biphenyl (PBB) in men from Greenland, Poland and Ukraine

Many brominated flame retardants (BFRs)—including polybrominated diphenyl ethers (PBDEs)—have been shown to persist in the environment, and some have been associated with adverse health effects. The aim of the present study was to quantify serum concentrations of common brominated flame retardants in Inuit men from across Greenland, and in men from Warsaw, Poland and Kharkiv, Ukraine. Serum was sampled between 2002 and 2004 from men 19 to 50years of age. 299 samples were analyzed for BDE-28, 47, 99, 100, 153, 154 and 183 and the brominated biphenyl BB-153 using gas chromatography–high resolution mass spectrometry. BDE-47 and BDE-153 were detected in more than 95% of samples from all three populations. All other congeners, except BDE-154, were detected in more than 70% of samples from Greenland; lower detection frequencies were observed in Polish and Ukrainian samples. Concentrations of individual congeners were 2.7 to 15 fold higher in Greenlandic relative to Polish and Ukrainian men. Geometric mean concentrations of the sum of the most abundant PBDEs of the Penta-BDE commercial mixture (BDE-47, 99, 100, 153 and 154) were 6.1, 1.7 and 0.87ng/g lipids in the Greenlandic, Polish and Ukrainian men, respectively. Furthermore, significant geographical differences in BFR concentrations were observed within Greenland. Principal component analysis revealed distinct clustering of samples by country of origin. The associations between ΣPBDEs and age were inconsistent, varying from no association in Greenlandic and Polish study populations to a U-shaped relationship in Ukrainians. We report BFR levels for three populations for which sparse biomonitoring data exists.

Dioxin-like activity in sediments from Tai Lake, China determined by use of the H4IIE-luc bioassay and quantification of individual AhR agonists

Deterioration of the general ecosystem and specifically quality of the water in Tai Lake (Ch: Taihu), the third largest freshwater in China, is of great concern. However, knowledge on status and trends of dioxin-like compounds in Tai Lake was limited. This study investigated AhR-mediated potency and quantified potential aryl hydrocarbon receptor (AhR) agonists in sediments from four regions (Meiliang Bay, Zhushan Lake, Lake Center, Corner of Zhushan Lake, and Meiliang Bay) of Tai Lake by use of the in vitro H4IIE-luc, cell-based, transactivation, reporter gene assay, and instrumental analysis. Concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (Bio-TEQs) in sediments ranged from less than the limit of detection to 114.5 pg/g, dry weight, which indicated that organic extracts of sediments exhibited significant AhR-mediated potencies. Results of the potency balance analysis demonstrated that acid-labile, dioxin-like compounds represented a greater proportion of concentrations of Bio-TEQs in sediments from Tai Lake. Concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents calculated as the sum of the product of concentrations of individual congeners and their respective relative potencies (Chem-TEQs) based on polycyclic aromatic hydrocarbons and/or polychlorinated biphenyls represented no more than 10% of the total concentrations of Bio-TEQs.

Environmental contamination of ready meals by polychlorinated biphenyls (PCBs)

The level of polychlorinated biphenyls (PCBs) contamination in ready meals was investigated to determine exposure compared to other foodstuffs. Chilled ready meals from nine categories (ambient, Chinese, Indian, Traditional UK, Italian, American Tex-Mex, Vegetarian and Organic), and three samples within each category were Soxhlet extracted in triplicate with hexane for 24 h, followed by a clean-up on deactivated silica gel. The cleaned extracts were concentrated to 1 ml under N2 gas and analyzed on gas chromatography mass spectrometry (GC-MS) for 7 target PCBs (congeners 28, 52, 101, 118, 153, 138, and 180). Individual congener concentrations ranged from non-detectable to 0.40 ng g−1 (wet weight). The cumulative concentration of all congeners (ΣPCBs) ranged between 0.20 and 1.00 ng g−1 (wet weight). These values translate into exposure levels of less than 1 μg kg−1day−1 for reference men and women of 70 and 57 kg, respectively. This preliminary study demonstrates that ready meals, like many other foods, are contaminated by PCBs and may represent an important route of human exposure given contemporary changes in consumer food choice. Even though low levels of contamination were observed, long-term exposure for population groups consuming a high volume of ready meals may have cause for concern regarding chronic health risks.

Optimization of selective pressurized liquid extraction for extraction and in-cell clean-up of PCDD/Fs in soils and sediments

This paper describes the development of methods for selective extraction of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from soils and sediments, using pressurized liquid extraction with in-cell clean-up (SPLE). Two binary solvent mixtures, viz. dichloromethane/n-heptane (DCM/Hp), and diethylether/n-heptane (DEE/Hp), were evaluated. The SPLE extraction conditions were optimized using central composite face (CCF) design. Three factors were investigated: extraction temperature (60–160°C), number of extraction cycles (1–3) and time per cycle (2–18min). The results showed that DCM/Hp (1/1, v/v) and DEE/Hp (1/2, v/v) were the best extraction solvent compositions and that the extraction temperature was a critical factor that needed careful optimization to achieve high extraction efficiency without co-extraction of sulfuric acid. Under the optimal conditions, the SPLE methods provided results with good accuracy and precision. For the sandy soil certified reference material (CRM-529) the quantification results ended up in the range 82–110% as compared to the concentrations obtained by a reference method based on Soxhlet extraction and external column clean-up. Furthermore, for a clay soil (CRM-530) and a sediment reference material (WMS-01), the accuracy (trueness) of the TEQ values were +11% (DCM/Hp) and +8% (DEE/Hp) for CRM-530, +8% and −7% for WMS-01, respectively. The individual congener concentrations also agreed well with the certified values. These findings show that SPLE is a promising method for combined extraction and clean-up of PCDD/Fs in soil/sediment samples.

Sources and distribution of polychlorinated-dibenzo- p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo- p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.

Bioanalytical and instrumental analysis of thyroid hormone disrupting compounds in water sources along the Yangtze River

Thyroid hormone (TH) agonist and antagonist activities of water sources along the Yangtze River in China were surveyed by a green monkey kidney fibroblast (CV-1) cell-based TH reporter gene assay. Instrumental analysis was conducted to identify the responsible thyroid-active compounds. Instrumentally derived l-3,5,3′-triiodothyronine (T3) equivalents (T3-EQs) and thyroid receptor (TR) antagonist activity equivalents referring to dibutyl phthalate (DBP-EQs) were calculated from the concentrations of individual congeners. The reporter gene assay demonstrated that three out of eleven water sources contained TR agonist activity equivalents (TR-EQs), ranging from 286 to 293 ng T3/L. Anti-thyroid hormone activities were found in all water sources with the TR antagonist activity equivalents referring to DBP (Ant-TR-EQs), ranging from 51.5 to 555.3 μg/L. Comparisons of the equivalents from instrumental and biological assays suggested that high concentrations of DBP and di-2-ethylhexyl phthalate (DEHP) were responsible for the observed TR antagonist activities at some locations along the Yangtze River.

Erratum: Polyhalogenated aromatic hydrocarbons and metabolites: Relation to circulating thyroid hormone and retinol in nestling bald eagles (Haliaeetus leucocephalus)

On page 1306, right-hand column, “∑PCB concentration was about 15,000 ppb”, should be replaced with “∑PCB concentration was about 15 ppb”, so that the sentence correctly reads: “Indeed, our average ∑PCB concentration was about 15 ppb, whereas our average ∑OH-PCB concentration was about 0.7 ppb, with the relative concentrations of individual congeners being somewhat similar.” Also, Figure 3 (top graph), the units of the contaminant concentration should be “Log ppb” instead of “Log ppm” (see revised figure below). Total thyroxine (TT4; top) decreased and total triiodothyronine (TT3; bottom) increased with contaminant concentrations for nestling bald eagles collected in 2003. Relationships are shown for contaminants selected in lowest Akaike's information criterion models. In upper graph, squares represent CB153, circles represent sum polychlorinated biphenyls (∑PCB), and triangles represent 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (p,p′-DDE). Dashed line represents linear CB153, black solid line represents linear ∑PCB, and gray solid line represents linear p,p′-DDE. OH-PBDE = hydroxylated polybrominated diphenyl ether.

Polybrominated Diphenyl Ether (PBDE) Flame Retardants and Thyroid Hormone during Pregnancy

BackgroundHuman exposure to polybrominated diphenyl ether (PBDE) flame retardants has increased exponentially over the last three decades. Animal and human studies suggest that PBDEs may disrupt thyroid function. Although thyroid hormone (TH) of maternal origin plays an essential role in normal fetal brain development, there is a paucity of human data regarding associations between exposure to PBDEs and maternal TH levels during pregnancy.ObjectivesOur goal was to determine whether PBDE serum concentrations are associated with TH levels in pregnant women.MethodsWe measured the concentration of 10 PBDE congeners, free thyroxine (T4), total T4, and thyroid-stimulating hormone (TSH) in 270 pregnant women around the 27th week of gestation.ResultsSerum concentrations of individual PBDE congeners with detection frequencies > 50% (BDEs 28, 47, 99, 100, and 153) and their sum (∑PBDEs) were inversely associated with TSH levels. Decreases in TSH ranged between 10.9% [95% confidence interval (CI), −20.6 to 0.0] and 18.7% (95% CI, −29.2 to −4.5) for every 10-fold increase in the concentration of individual congeners. Odds of subclinical hyperthyroidism (low TSH but normal T4) were also significantly elevated in participants in the highest quartile of ∑PBDEs and BDEs 100 and 153 relative to those in the first quartile. Associations between PBDEs and free and total T4 were not statistically significant. Results were not substantially altered after the removal of outliers and were independent of the method used to adjust for blood lipid levels and to express ∑PBDEs.ConclusionsResults suggest that exposure to PBDEs is associated with lower TSH during pregnancy. Findings may have implications for maternal health and fetal development.

Passerine Exposure to Primarily PCDFs and PCDDs in the River Floodplains Near Midland, Michigan, USA

House wren (Troglodytes aedon), tree swallow (Tachycineta bicolor), and eastern bluebird (Sialia sialis) tissues collected in study areas (SAs) downstream of Midland, Michigan (USA) contained concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) greater than in upstream reference areas (RAs) in the region. The sum of concentrations of PCDD/DFs (ΣPCDD/DFs) in eggs of house wrens and eastern bluebirds from SAs were 4- to 22-fold greater compared to those from RAs, whereas concentrations in tree swallow eggs were similar among areas. Mean concentrations of ΣPCDD/DFs and sum 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (ΣTEQsWHO-Avian), based on 1998 WHO avian toxic equivalency factors, in house wren and eastern bluebird eggs ranged from 860 (430) to 1500 (910) ng/kg wet weight (ww) and 470 (150) to 1100 (510) ng/kg ww, respectively, at the most contaminated study areas along the Tittabawassee River, whereas mean concentrations in tree swallow eggs ranged from 280 (100) to 760 (280) ng/kg ww among all locations. Concentrations of ΣPCDD/DFs in nestlings of all studied species at SAs were 3- to 50-fold greater compared to RAs. Mean house wren, tree swallow, and eastern bluebird nestling concentrations of ΣPCDD/DFs and ΣTEQsWHO-Avian ranged from 350 (140) to 610 (300) ng/kg ww, 360 (240) to 1100 (860) ng/kg ww, and 330 (100) to 1200 (690) ng/kg ww, respectively, at SAs along the Tittabawassee River. Concentrations of ΣTEQsWHO-Avian were positively correlated with ΣPCDD/DF concentrations in both eggs and nestlings of all species studied. Profiles of relative concentrations of individual congeners were dominated by furan congeners (69–84%), primarily 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran, for all species at SAs on the Tittabawassee and Saginaw rivers but were dominated by dioxin congeners at upstream RAs.Electronic supplementary materialThe online version of this article (doi:10.1007/s00244-009-9416-6) contains supplementary material, which is available to authorized users.

Concentrations of polychlorinated biphenyls in blood collected from Yusho patients during medical check-ups performed from 2004 to 2007.

To elucidate the exposure levels of polychlorinated biphenyls (PCBs) for Yusho patients, we conducted a congener-specific analysis of polychlorinated biphenyls (PCBs) in blood collected from 242, 237, 300, and 96 Yusho patients during medical check-ups performed from 2004 to 2007, respectively, and in samples from 74, 113, 125, and 148 Yusho-suspected persons during those same years, respectively, and compared the individual congener concentrations of PCBs among the groups of Yusho patients, Yusho-suspected persons, and normal controls with the concentrations previously reported. Among the 209 PCB congeners, 8 congeners of mono-ortho PCBs and 56 congeners of non-dioxin-like PCBs were identified in the blood of Yusho patients and Yusho-suspected persons. Among the PCB congeners measured in the present study, hexaCB-153, hexaCB-138, heptaCB-180, and heptaCB-182/heptaCB-187 showed high ratios to total concentrations of 64 PCB congeners detected in the blood of Yusho patients and Yusho-suspected persons from 2004 to 2007, and the profiles of the major congeners were the same as those obtained in normal controls. With respect to the minor congeners of PCBs, several differences were observed among the three groups. The sums of the concentrations of 64 PCB congeners in the blood of Yusho patients from 2004 to 2007 were 645, 760, 667, and 510 ng g(-1) lipid for each year, respectively, and the concentrations were 1.5, 1.8, 1.5, and 1.2 times higher than those of normal controls for each year, respectively. Those of the Yusho-suspected persons were approximately 0.8, 1.1, 0.9, and 1.0 times higher than those of normal controls for each year, respectively. The ratios of heptachlorinated biphenyls (heptaCBs) to the total concentrations of 64 PCB congeners in the blood of Yusho patients and Yusho-suspected persons from 2004 to 2007 tended to be slightly higher than those in the normal controls. From the results comparing the concentrations of 64 PCB congeners in the blood between Yusho patients and normal controls, the concentrations of hexaCB-156, hexaCB-157, heptaCB-181, and heptaCB-189 for Yusho patients were 3.4, 3.8, 3.9, and 3.8 times, respectively, 3.9, 4.1, 3.9, and 4.4 times, respectively, 3.6, 3.9, 5.0, and 4.1 times, respectively, and 2.3, 2.5, 2.7, and 2.9 times higher than those of the normal controls for each year from 2004 to 2007, respectively. These results indicated that Yusho patients still have higher concentrations of hexaCB-156, hexaCB-157, heptaCB-181, and heptaCB-189 in their blood than do unaffected people, even though over 35 years have passed since the outbreak of Yusho. These four congeners can therefore be considered to be the most important congeners for evaluating the PCBs exposure of Yusho patients.

Transfer and Accumulation of Persistent Organochlorine Compounds from Bovine Dams to Newborn and Suckling Calves

The maternal-fetal and neonatal transfers of polychlorinated dibenzo- p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) were measured in the blood and milk of dams and in the blood of newborn and suckling calves. Calf blood toxic equivalent quantities (TEQs) were drastically increased by suckling. Blood concentrations of individual congeners were greater in suckling calves than in newborn calves, excluding octachlorodibenzo- p-dioxin (O 8CDD); O 8CDD did not readily transfer to milk but was readily absorbed by the gastrointestinal tract and remained in systemic circulation longer than other congeners. Congener concentrations in milk were correlated with maternal blood levels, and those in suckling calf blood were dependent on their concentrations in milk. These results suggest that neonatal calves absorb more lipophilic organochlorine compounds than prenatal fetuses, that those compounds that are transferred from dams to calves are associated not only with lipid transport but also with other carriers, and that the distribution of congeners is structure-dependent.

Persistent Organochlorine Residues in Livers of Six Species of Ciconiiformes (Aves) from Spain

Liver samples of 42 birds belonging to 6 species of Ciconiiformes (grey heron (n = 17), little egret (n = 12), cattle egret (n = 1), glossy ibis (n = 1), little bittern (n = 1), and white stork (n = 10)), collected from two different zones of Spain (Ebro Delta and Madrid) in 1992–1997, were analyzed for organochlorine pesticides and PCBs. ΣPCBs (sum of concentrations of individual congeners), p,p′-DDE, HCB, γ-HCH, and heptachlor epoxide were the most prevalent residues detected in all samples (occurrence > 95%). There were no statistically significant differences in organochlorine levels between grey herons and little egrets, while levels of ΣPCBs, p,p′-DDE, HCB, γ-HCH, and heptachlor were significantly lower for white storks. These results could be explained by the different habitat of these species, aquatic in the Ebro Delta (grey herons, little egrets) and dry in Madrid (white stork), and their diverse feeding habits.

Polychlorinated Biphenyl Concentrations, Congener Profiles, and Ratios in the Fat Tissue, Eggs, and Plasma of Snapping Turtles (Chelydra s. serpentina) from the Ohio Basin of Lake Erie, USA

Concentrations and profiles of polychlorinated biphenyls (PCBs) were determined in three tissues of adult snapping turtles (Chelydra serpentina serpentina) from six locations in the Ohio Basin of Lake Erie to characterize tissue variation and geographic trends. The locations included the Ohio Areas of Concern, i.e., the Ashtabula, Black, and Maumee Rivers; the Ottawa River near Toledo; and two reference sites. Mean total PCBs were greatest in turtles from the Ottawa River followed by the Maumee, Ashtabula, and Black Rivers. All three types of samples-fat tissue (FT), eggs, and plasma-showed the same geographic trend in PCB levels. On a wet-weight basis, mean concentrations ranged from 2,148 to 18,669 ng/g in FT, from 183 to 3,683 ng/g in eggs, and from 18 to 201 ng/g in plasma. Across all sites, total PCB concentrations between the tissues were significantly correlated (0.001 < p < 0.005; Pearson correlation coefficient (r ( P )) was between 0.720 and 0.954). Two distinctly different profiles with respect to relative congener and homologue concentrations were found among the sites. One that included four of the six sites examined was characterized by hexa-chlorobiphenyl (hexa-CB) dominance followed by hepta-CBs, with PCBs no. 138 + 163, 153 + 132 + 105, and 180 being the most abundant congeners. The second profile, specific for turtles from the Ottawa River, was different from the first in that tetra-CBs were the most abundant congeners followed by hexa-CBs. Analysis of variance (ANOVA) indicated significant intertissue differences in the PCB homologue profiles, i.e., FT had a higher percentage of hepta-, octa-, and nona-CBs compared with eggs and plasma, whereas eggs showed a higher percentage of hexa-CBs. At any listed location, FT, eggs, and plasma had the same congener profile. An intertissue distribution of lipid-normalized individual congener concentrations examined by regression analyses revealed significant egg-FT, egg-plasma, and FT-plasma relations for >40 congeners (0.001 < p < 0.05). The distribution ratios determined for these congeners from the slope of the regression lines averaged 1.235 +/- 0.279, 0.430 +/- 0.170, and 0.387 +/- 0.115, respectively. The plasma wet weight-FT lipid-normalized concentration ratios for these congeners averaged 0.012 +/- 0.006. Both egg-FT and plasma wet weight-FT lipid-normalized ratios regressed against log K(ow) showed significant decreases, with increasing log K(ow), indicating greater accumulation of highly chlorinated congeners in FT than in other compartments. The estimated 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents ranged from 0.007 ng/g at reference sites to 0.060 ng/g at contaminated sites and from 0.099 to 1.992 ng/g in plasma and eggs, respectively. In both plasma and eggs, coplanar-CBs were the major contributors to total toxic equivalents (TEQs). Eggs from all contaminated sites had TEQs that exceeded the lowest observed effect level TEQs proposed for bald eagle chicks, in addition to high SigmaPCB levels at some of these sites, especially the Ottawa and Maumee River sites, indicate potentially increased risk to turtles and possibly other wildlife species inhabiting these ecosystems. Significant correlations of total PCBs and individual congeners between FT, eggs, and plasma indicate that blood sampling can provide a good nonlethal measure of PCB exposure and can be used to monitor environmental contamination.

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.