Polychlorinated biphenyl residues in deep-sea fish from Mediterranean Sea

Polychlorinated biphenyls including coplanar congeners were measured in the liver of different species of skates and ghostsharks. The mean concentrations of PCBs in skates (314 ng/g wet wt) were comparable with those in ghostsharks (285 ng/g wet wt). The specific analysis of PCB congeners in skates hepatic tissue revealed a profile dominated by hexa-, penta-, and heptachlorinated congeners followed by trichlorobiphenyls, tetra- and decachlorobiphenyls. A different profile dominated by hexa-, tri-, and pentachlorinated congeners, followed by heptachlorobiphenyl and decachlorobiphenyls was found in ghostsharks liver. The estimated 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) of coplanar PCBs in skates and ghostsharks were 0.48 and 0.33 pg/g wet weight, respectively, with mono-ortho congeners PCB105, 118 and 156 contributing more than 90% to the TEQs.     

Dioxins and PCBs in game animals: Interspecies comparison and related consumer exposure

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (DL-PCB) and non-dioxin-like polychlorinated biphenyls (NDL-PCB) are ubiquitous, persistent toxic compounds that are highly bioaccumulative in nature. Wild-living animals are vulnerable to the negative impacts of human activity. Dioxins and PCBs enter the animal organisms through foraging. Due to the toxicological threat, much attention is paid to these compounds worldwide. The aim of this study was to determine the dioxin contamination status of three game animal species (red deer, roe deer, and wild boar) and compare the PCDD/F and PCB congener bioaccumulation in the muscles, abdominal fat and liver. The chemical analysis was performed by the isotope dilution technique (IDMS) with high-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC/HRMS). Dioxins and PCBs were found in specimens collected from all studied species, suggesting the presence of the test compounds in the environment of the animals. The highest concentrations were found in the livers of all animals. The toxic equivalent (TEQ) levels in the muscles, adipose tissue and liver were in the order red deer > roe deer > wild boar. PCDD/Fs were the dominant congeners in TEQ value. For all tested species, the dominant contributors to the total WHO-TEQ were PCB-126, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD. Among the PCDD/F congeners in the deer tissues, OCDD, OCDF and 2,3,4,7,8-PeCDF were dominant, while in wild boar, OCDD, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCF occurred in the highest amounts. Among PCBs, PCB-105, 118, 156, 138, 153 and 180 were dominant in all species, but with different levels. The regular consumption of muscle meat from game animals should not cause unacceptable dioxin intake above the Tolerable Weekly Intake (TWI) value for children and adults. However, liver consumption should be avoided, especially by children and pregnant or lactating women. High consumption of contaminated liver may cause dioxin intake at levels up to 300% of TWI for adults and up to 700% TWI for children.     

Unexpected high PCB and total DDT levels in the breeding population of red kite (Milvus milvus) from Doñana National Park, south-western Spain

This study provides information on the current status of contamination by organochlorines (DDTs, PCBs, PCDDs and PCDFs) in the declining red kite (Milvus milvus L.) population breeding in the Do?ana National Park (DNP), south-western Spain. Analyses were performed in addled eggs collected between 1999 and 2001. DDE concentrations ranged from 0.1 to 33.5 microg/g ww, representing more than 86% of the total DDTs. Of the samples studied, 50% showed DDE levels above those associated with reproductive impairment in other raptor species. Concentrations of ortho PCBs (average 36.8 microg/g ww+/-37.7) in 50% of the eggs were much higher than levels reported to cause reduced hatching success, embryo mortality, and deformities in birds (>20 microg/g ww). It is remarkable that average ortho PCB and DDE concentrations showed an increase of one order of magnitude compared to previous data for the species during the 80s. Total PCDD/Fs showed levels in the low pg/g range (7.2-42 pg/g ww), having PCDDs and PCDFs similar contributions in most samples. Total mean TEQs were 238 pg/g (ww), being the range 7.02-667 pg/g (ww). Spatial variation within DNP was observed for PCBs, DDTs, as well as for TEQs. Since some eggs exceeded the NOEL (67%) and LOEL (33%) reported for other raptor species, we would expect the red kite to experience detrimental effects to dioxin-like toxicity. Our results suggest that organochlorine contaminants should be regarded as an element of concern in the population under study, in addition to other conservation problems already reported. Further investigations should be undertaken to identify potential sources of these chemicals in DNP, and to find out if organochlorine contamination is present in other predator species in the area, as well as their potential health effects on individuals and/or populations.     

Temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in mothers' milk from Sweden, 1972–2011

Temporal trends of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in mothers' milk are still quite rare. Data are particularly scarce when it comes to concentrations from the last decade, 2000 and onwards. The aims of the present study were to assess temporal trends of PCDD, PCDF and DL-PCB in mothers' milk from Stockholm, 1972–2011 and to compare the results with previous analysis of some of the older samples.The samples were analyzed by high resolution GC/MS and results were statistically evaluated for the periods, 1972–2011 and 2002–2011. The rate of which ∑PCDDs, ∑DL-PCBs and the ∑TEQ are decreasing (on pg/g fat WHO-TEQ2005) is higher in the last decade compared to the 40 year period, 1972–2011. A similar trend is indicated, but not confirmed, for ∑TEQ of PCDFs, probably due to too many PCDF congeners below LOQ in the period 2002–2011. Concentrations of ∑PCDDs, ∑PCDFs, ∑DLPCBs and ∑TEQ, all expressed as pg/g fat on TEQ-WHO2005-basis, show a statistically significant decline over time, 5.8–6.8% per year, 1972–2011. The last ten years the annual declines for ∑PCDDs, ∑DL-PCBs and ∑TEQ are 9.2–11% and for ∑PCDF, 5.4%. Congener specific trend analysis, 2002–2001, of PCDDs and DL-PCBs showed the same pattern, while the PCDF congeners showed no such general trend. The results from the re-analysis showed good agreement with slightly lower ∑TEQ1998 pg/g fat concentrations in six out of seven samples and mean difference of 13% in ∑TEQ1998. The study shows that time series can be elongated from previous studies, as long as the sample population remains the same.     

Toxicokinetic study of dioxins and furans in laying chickens

Since foodstuffs from animal origin and particularly poultry products have been pointed out several times as reservoir of dioxins and related compounds, notably in Belgium few years ago, food chain safety issues appeared. Although food chain contamination incidents occurred many times through contaminated feedstuffs consumption in commercial chicken farms, very few studies have been carried out on transfer of dioxins and related compounds from commercial feed to hens. The present work continues a preliminary study on dioxin transfer in laying chickens carried out in our lab and available on-line on November 2004 in Environment International. In this work, absorption of dioxins were not preferential for 2,3,7,8-substituted congeners, increase with increasing number of chlorines, and was not linearly dependent of the octanol/water partition. Only 2,3,7,8-congeners were found in all organs studied, and these latter showed the same congener profile and similar lipid-normalized concentration, except for the liver. Abdominal fat and liver seemed to be the major storage sites and the liver preferentially retained highly chlorinated congeners. Unfortunately in this previous trial, laying process stopped very early for unknown reason leading to a considerable lost of information. In the present toxicokinetic study, more complete gastrointestinal absorption, excretion in eggs and bioaccumulation of dioxins in different tissues were investigated in chickens fed for 14 weeks with a 9 ng TEQ/kg contaminated feed. Stable levels were reached after 7 weeks in excreta and 9 weeks in eggs. During the whole trial, gastrointestinal absorption ranged between 41% and 91% depending on the congener. At steady state conditions, excretion of 1,2,3,4,6,7,8-HpCDD, OCDD, 1,2,3,4,6,7,8-HpCDF and OCDF exceeded 100% demonstrating excretion from tissues of these congeners which were also the most abundant in feed. 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 2,3,4,6,7,8-HxCDF seemed to be metabolized more efficiently. Lipid adjusted concentrations and pattern were unexpectedly similar in the abdominal fat and the liver. On the contrary, eggs and breast muscles showed different pattern with higher level for high chlorinated congeners. When extrapolating our results, we found that a feed containing 0.750 ng TEQ/kg of dioxins (European norm for feedstuff) would cause a level lower than the maximum threshold level of 3 pg TEQ/g fat for chicken eggs fixed by European Communities. Nevertheless, a concentration lower than 0.6 ng TEQ/kg in feed would be needed to produce breast muscles less contaminated than 2 pg TEQ/g fat authorized in European.     

Organochlorine and heavy metals in newborns: Results from the Flemish Environment and Health Survey (FLEHS 2002–2006)

To collect regional information on internal levels of pollutants in humans in Flanders, 1196 mother–child pairs were systematically recruited in 2002–2003 via 25 maternities across Flanders. Cd, Pb, PCB congeners 118, 170, 138, 153 and 180, p,p′-DDE — a key metabolite of DDT- and hexachlorobenzene (HCB) were measured in cord blood or plasma. Cd was detected in 64% of the samples (geometric mean 0.21 µg/L cord blood). p,p′-DDE (110 ng/g plasma lipids) and Pb (14.7 µg/L blood), were measurable in nearly all samples. The individual PCB congeners could be detected in 40 to 81% of the newborns (138 + 153 + 180 = 64.4 ng/g plasma lipids). HCB (18.9 ng/g plasma lipids) and dioxin-like compounds measured by DR-CALUX® (23 pg CALUX-TEQ/g lipids) were above detection limit in more than 75% of the samples. Age and smoking habits of the mothers, did not influence the cord blood Pb and Cd levels. The organochlorines increased 4 to 9% per year of the mother's age (partial R² = 0.05 to 0.22). Mothers had 2.6% less PCBs in cord blood (partial R² = 0.02) for each unit increase in pre-pregnancy BMI. Season of delivery, breastfeeding previous children or consumption of local dairy products, were minor determinants. Up to 20% of the variability in organochlorine concentrations was explained by residence area. It was concluded that the place of birth in Flanders is an important determinant of the load of pollutants measured at the start of life. This underlines the validity of human biomonitoring on (relatively) small geographical scale.     

Distribution of PCBs, HCHs and DDTs, and their ecotoxicological implications in Bay of Bengal, India

Analyses of environmentally persistent pollutants like polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) isomers, and dichlorodiphenyltrichloroethane (DDT) and its metabolites in seawater and sediment samples collected from six locations along the east coast of India were carried out using High-Resolution Gas Chromatograph with High-Resolution Mass Spectrometer (HRGC-HRMS). Sediment and water from Chennai harbour and Cuddalore fishing harbour contained higher concentration of all the compounds. The highest concentration (6570 pg/g dry weight) of total PCB was found in sediment from Chennai harbour followed by sediments sampled in Chennai (opposite to Cooum River mouth) (505 pg/g), Cuddalore fishing harbour (335 pg/g) and Mandapam (251 pg/g). Concentrations in other locations were two orders of magnitude lower than Chennai harbour. A distinct PCB distribution pattern in sediment was observed between harbours and other locations. Greater concentrations of tetra-, penta- and hexachlorobiphenyls were observed in sediments of harbours and opposite to Cooum river mouth, but in other locations lower chlorinated biphenyls (di, tri and tetra-) were more. In seawater, HCH concentration was greater than DDT, but it was quite opposite in sediments. Elevated levels of DDT in sediment were observed only at highly populated urban locations, reflecting the local usage and input of this pesticide. Based on sediment/water quality criteria/guidelines, some coastal locations of the Bay of Bengal could be designated as being polluted by DDTs and gamma-HCH (lindane), but not by PCBs. This investigation reveals the declining trend on the environmental burden of persistent pesticides in Indian marine environment. Data on the organochlorine concentrations found in this survey can be used as reference levels for future POPs monitoring programme.     

Characterisation of chlorinated,brominated and mixed halogenated dioxins,furans and biphenyls as potent and as partial agonists of the Aryl hydrocarbon receptor

The Aryl hydrocarbon receptor (AhR) binds a variety of chlorinated and brominated dioxins, furans and biphenyls. Mixed halogenated variants have been recently identified in food at significant levels but full characterisation requires potency data in order to gauge their impact on risk assessment. Rat H4IIE and human MCF-7 cells were treated with various mixed halogenated ligands. Antagonist properties were measured by treating cells with various concentrations of TCDD in the presence of EC₂₅ of the putative antagonist. Measurement of CYP1A1 RNA was used to quantify the potency of agonism and antagonism. The PXDDs were found to be slightly less potent than the corresponding fully chlorinated congeners with the exception of 2-B,3,7,8-TriCDD which was 2-fold more potent than TCDD. PXDFs and non-ortho-PXBs were found to be more potent than their chlorinated congeners whilst several mono-ortho-substituted PXBs were shown to have partial agonistic properties. REPs were produced for a range of mixed halogenated AhR-activating ligands providing a more accurate estimation of potency for risk assessment. Several environmentally abundant biphenyls were shown to be antagonists and reduce the ability of TCDD to induce CYP1A1. The demonstration of antagonism for AhR ligands represents a challenge for existing REP risk assessment schemes for AhR ligands.     

Levels and congener pattern of polychlorinated biphenyls in the blubber of the Mediterranean bottlenose dolphins Tursiops truncatus

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169) and mono-ortho (105, 118, 156) coplanar congeners were determined in the blubber of nine bottlenose dolphins (Tursiops truncatus) stranded along the Eastern Italian coast. The total PCB concentrations ranged from 3534 to 24375 ng/g wet wt. The PCB profile was dominated by congeners 138 and 153 collectively accounting for 55% of the total PCB concentrations. Among the most toxic congeners the order of abundance was 126>169>77. The mean total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalent of six coplanar PCBs in the blubber of bottlenose dolphins was 45596 pg/g. Non-ortho congeners contributed greater to the 2,3,7,8-TCDD toxic equivalents than mono-ortho members. Particularly, PCB 126 was the major contributor to the estimated toxic potency of PCBs in dolphins.     

Levels of PCDD/Fs and trace elements in superficial soils of Pavia Province (Italy)

Trace elements and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soils from rural and light-industrialized sites (n=168) of Province of Pavia (Northern Italy). Most of the trace element values fit in typical ranges of concentrations in soils and are similar to the ones reported for rural sites in Italy or sites with no direct anthropogenic impact. Total concentrations of 2,3,7,8 chlorine substituted PCDD/Fs in superficial soils ranged between 24.4 and 1287 pg g(-1) dw (0.5-28.9 pg WHO(98)-TEQ g(-1) dw). The North Eastern part of the Province presented significantly higher levels (p<0.001) than the rest of the Province for As, Cd, Hg, Pb, Zn and PCDD/Fs. While the existence of a defined heavy metal polluting source for this specific site has been suggested, in the case of PCDD/Fs, profiles were not linked to any specific emission source fingerprint. In the whole extension of Pavia Province, OCDD/F dominated the 2,3,7,8 chlorine substituted congener soil pattern, followed by the 1,2,3,4,6,7,8 hepta-CDD/F congener. Principal Component Analysis (PCA) showed that this profile could not be associated to any described PCDD/F emission source fingerprint and was relatively similar to the baseline deposition of sites with no direct impact of PCDD/F emission sources independently of land use.     

Persistent organic pollutants (PCBs and DDTs) in small size specimens of bluefin tuna (Thunnus thynnus) from the Mediterranean Sea (Ionian Sea)

The concentration levels and pattern distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides (DDTs), were investigated in liver of small size specimens of bluefin tuna (Thunnus thynnus) from Mediterranean Sea (Ionian Sea). PCB concentrations (average: 526 ng g(-1) lipid wt) were comparable with DDT levels (average: 435 ng g(-1) lipid wt). The specific analysis of PCB congeners revealed a profile dominated by hexa-, penta- and heptachlorinated congeners, while among DDTs, the compounds with the higher concentration was p,p'-DDE, constituting 91.9% of the total DDT. The total 2,3,7,8-TCDD toxic equivalent (TEQs) of coplanar PCBs, including mono- and non-ortho congeners, was 0.55 pg g(-1) wet weight with. The congeners with highest TEQs values were non-ortho congeners followed by mono-ortho ones.     

Dioxin-like compounds in agricultural soils near e-waste recycling sites from Taizhou area, China: chemical and bioanalytical characterization

The crude recycling of electronic and electric waste (e-waste) is now creating a new set of environmental problems especially in developing countries such as China. The present study aimed to characterize the dioxin-like compounds in Taizhou area, one of the largest e-waste recycling centers in China, using both chemical analysis and in vitro bioassay. Agricultural soil samples were screened for aryl hydrocarbon receptor (AhR) activity with EROD bioassay in H4IIE cells, and the concentrations of the target AhR agonists including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were determined by instruments. The bioassay-derived TCDD equivalents (TEQ(bio)) and the chemical-calculated TCDD equivalents (TEQ(cal)) were then compared, and mass balance analysis was conducted to identify the contributors of the observed response. Raw soil extracts from all locations induced significant AhR activities, where the TEQ(bio) ranged from 5.3 to 210 pg/g dry weight soil (pg/g dw). The total concentrations of 17 PCDD/Fs, 36 PCBs and 16 PAHs varied from 210 to 850 pg/g dw, 11 to 100 ng/g dw, and 330 to 20,000 ng/g dw, respectively. Profile characterization of the target analytes revealed that there were similar sources originating from the crude dismantling of electric power equipments and the open burning of e-waste. There was a significant relationship between TEQ(cal) and TEQ(bio) (r=0.99, p<0.05). Based on the mass balance analysis, PCDD/Fs, PCBs and PAHs could account for the observed AhR responses in vitro elicited by soil extracts, though their respective contributions varied depending on sample location. In this study, the combination of chemical analysis and bioanalytical measurements proved valuable for screening, identifying and prioritizing the causative agents within complex environmental matrices.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans pollution in China: sources, environmental levels and potential human health impacts

This review represents an assessment of the pollution status of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in China (the mainland, Hong Kong and Taiwan). During the past decades, seven PCDD/Fs pollution hotspots have been found: (a). Ya-er Lake, Hubei Province, with 'total PCDD/Fs' level reaching 177,427 pg g(-1) (dry weight) in lake sediments; (b). Chinese Schistosomiasis affected areas of Jiangxi Province with 33,660 pg g(-1) in soil; (c). e-waste recycling area of Yangtze River Delta, with 2726 pg g(-1) in paddy soil; (d). e-waste recycling area of Guiyu (eastern part of Guangdong Province), with 967,500 pg g(-1) in mixture of burnt residue and soil (the highest level among all hotspots); (e). Pearl River Delta with 2630 pg g(-1) in coastal sediment. (f). Kwun Tong, Victoria Harbour, Hong Kong with 10,999 pg g(-1) in coastal sediment; and (g). southern Taiwan with 606,000 pg g(-1) in soil near the vicinity of a pentachlorophenol manufacturing factory. The main sources of PCDD/Fs in China were formed from impurities during the production of polychlorophenol, hexachlorobenzene, polychlorinated biphenyls, organic chlorinated pesticide and triclosan. In addition, sources of PCDD/Fs included municipal waste incineration, mineral fuel usage, open burning of electronic waste and crop residues, industrial waste discharge and vehicle exhaust emission. Due to potential human health risks from long-term exposure to PCDD/Fs at these hotspots, body loadings of these contaminants should be monitored.     

Application of an improved method for the analysis of pesticides and their metabolites in the urine of farmer applicators and their families

As the annual use of pesticides in the United States has escalated, public health agencies have become increasingly concerned about chronic pesticide exposure. However, without reliable, accurate analytical methods for biological monitoring, low-level chronic exposures are often difficult to assess. A method for measuring simultaneously the urinary residues of as many as 20 pesticides has been significantly improved. The method uses a sample preparation which includes enzyme digestion, extraction, and chemical derivatization of the analytes. The derivatized analytes are measured by using gas chromatography coupled with isotope-dilution tandem mass spectrometry. The limits of detection of the modified method are in the high pg/L - low μg/L range, and the average coefficient of variation (CV) of the method was below 20% for most analytes, with approximately 100% accuracy in quantification. This method was used to measure the internal doses of pesticides among selected farmer applicators and their families. Definite exposure and elimination patterns (i.e., an increase in urinary analyte levels following application and then a gradual decrease to background levels) were observed among the farmer applicators and many of the family members whose crops were treated with carbaryl, dicamba, and 2,4-D esters and amines. Although the spouses of farm workers sometimes exhibited the same elimination pattern, the levels of the targeted pesticides or metabolites found in their urine were not outside the ranges found in the general U.S. population (reference range). The farmer applicators who applied the pesticides and some of their children appeared to have higher pesticide or metabolite levels in their urine than those found in the general U.S. population, but their levels were generally comparable to or lower than reported levels in other occupationally exposed individuals. These results, however, were obtained from a nonrandom sampling of farm residents specifically targeted to particular exposures who may have altered their practices because they were being observed; therefore, further study is required to determine if these results are representative of pesticide levels among residents on all farms where these pesticides are applied using the same application techniques. Using this method to measure exposure in a small nonrandom farm population allowed differentiation between overt and background exposure. In addition, the important role of reference-range information in distinguishing between various levels of environmental exposure was reaffirmed.     

Toxicokinetics of dioxins and other organochlorine compounds in Japanese people: Association with hepatic CYP1A2 expression levels

Concentrations of persistent organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in the liver and adipose tissue of Japanese cadavers were measured, and their toxicokinetics were examined in association with hepatic cytochrome P450 (CYP) 1A protein expression levels. Total 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were 66 ± 74 and 65 ± 57 pg/g lipid weight (mean ± S.D.) in the liver and adipose tissue, respectively. Total PCBs (sum of 62 congeners targeted), p,p′-dichlorodiphenyl-dichloroethylene (p,p′-DDE) and β-hexachlorocyclohexane (β-HCH) were detected at concentrations over 1 μg/g lipid in both tissues of some specimens. For most of the dioxin-like congeners, total PCBs, p,p′-DDE, oxychlordane, α- and β-HCH, hexachlorobenzene (HCB), and tris(4-chlorophenyl)methane (TCPMe), age-dependent increases in concentrations were found in the adipose tissue of males. No such age-dependent trend was observed in the liver, suggesting that there are different mechanisms underlying the hepatic concentrations of OCs. Immunoblot analyses indicated detectable expression of hepatic CYP1A2 protein, whereas no CYP1A1 protein was detected. The CYP1A2 expression levels were positively correlated with concentrations (on wet weight basis) of 2,3,4,7,8-P₅CDF, the dominant TEQ-contributed congeners in the liver, indicating the induction of this CYP. Hepatic CYP1A2 protein levels were strongly correlated with the liver to adipose concentration (L/A) ratios of PCDD/F congeners with more than 5 chlorine atoms. Together with higher concentrations of the congeners in the liver than in the adipose tissue, the observation on L/A ratios of highly chlorinated PCDD/Fs suggests that induced hepatic CYP1A2 protein is involved in their sequestration in this human population, as observed in model animals (rodents). Nonetheless, the magnitude of hepatic sequestration (L/A ratio) of PCDD/Fs in this human population was lower than in other mammals and birds, reported previously. This study emphasizes the fact that toxicokinetics of some OCs can be affected at least partly by CYP1A2 protein levels in humans. For the extrapolation of their toxicokinetics from model animals to humans, knowledge on the induction and sequestration potencies of CYP1A is necessary.     

Organohalogen and metabolically-derived contaminants and associations with whole body constituents in Norwegian Arctic glaucous gulls

Comprehensive surveys of organohalogen contaminants have been conducted in various tissues and blood of glaucous gulls (Larus hyperboreus), a top scavenger-predator species in Svalbard in the Norwegian Arctic. However, the physico-chemical properties of organohalogens (e.g., type and degree of halogenation and the presence or absence of additional phenyl group substituents) that may influence toxicokinetics, and subsequently tissue-specific accumulation, have yet to be studied in this species. We investigated the concentrations, total body burdens, and compositional patterns of legacy chlorinated compounds (PCBs and chlordanes (CHLs)), metabolically-derived PCBs (methylsulfonyl (MeSO(2))- and OH-PCBs), brominated flame retardants (polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), total-hexabromocyclododecane (HBCD)), and PBDE metabolites and/or naturally-occurring compounds with similar structures (MeO- and OH-PBDEs) in liver, blood and whole body homogenate samples of adult glaucous gulls (n=19) from Svalbard. Further, we examined the distribution of these organohalogens and metabolites in relation to whole body composition of glaucous gulls, i.e., the total water, protein, lipid and mineral contents in whole homogenate carcasses. The total body burden of organohalogens and metabolites in glaucous gulls ranged between 3.3 and 33.0 mg. Compound class distribution showed that the relative proportions of sum (Sigma) OH-PCB and SigmaOH-PBDE to the total organohalogen concentrations were significantly highest in blood. Conversely, the SigmaCHL and SigmaPCB showed generally higher proportions in the lipid-rich liver as well as in whole body homogenates. No significant difference in the compositional patterns of individual congeners/compounds was found among tissues/blood, with the exception of the classes comprised of less polar brominated compounds (PBDEs, PBBs and total-(alpha)-HBCD). Total proteins isolated from the whole body homogenates of glaucous gulls were significantly associated to the proportions of SigmaOH-PCB and SigmaPBDE. A non-significant positive association was found between total lipids and the SigmaPCB proportions. The present study suggests that both protein association and lipid solubility are important concomitant factors to be considered in the toxicokinetics and fate of contaminants as a function of chemical structure and properties, e.g., chlorination, bromination and the presence of other phenyl substituents such as OH group. An enhanced, selective retention of these organohalogen classes in given tissues/body compartments may thus lead to site-specific toxicological actions and adverse effects in the highly-contaminated Svalbard glaucous gulls.     

Dechlorane plus and possible degradation products in white stork eggs from Spain

The occurrence of the emerging chlorinated flame retardant Dechlorane Plus (DP) and three of its possible degradation products was investigated in white stork eggs from two colonies in Spain. The average DP concentrations were 401 pg/g wet weight (w.w.) for the urban/industrial colony and 105 pg/g w.w. for the rural colony. One possible degradation product, anti-[DP-1Cl], was found in approximately 10% of the samples. No significant stereoisomer enrichments were detected in any colony based on the average anti-DP fractional abundances found which agrees with previous studies in herring gulls. The relationship between DP and PBDE contents in both colonies was explored leading to different scenarios, i.e. no correlation was found in the urban colony but they were statistically correlated in the rural colony. To the best of our knowledge, this is the first study to report DP in a species from a terrestrial food web, and also to report a DP degradation product in biota.     

Determination of polybrominated diphenyl ethers in human semen

Some persistent organic pollutants (POPs) have been found in human semen but until this point it was unclear whether polybrominated diphenyl ethers (PBDEs) could be detected in human semen. In this study, PBDEs were found for the first time in human semen samples (n = 101) from Taizhou, China. The concentrations of total PBDEs (∑ PBDEs) varied from 15.8 to 86.8 pg/g ww (median = 31.3 pg/g ww) and 53.2 to 121 pg/g ww (median = 72.3 pg/g ww) in semen and blood samples, respectively. The ∑ PBDE level in semen was about two times lower than in human blood, which was different in the distribution in the two matrices from other POPs. A correlation of ∑ PBDE concentration was found between paired semen and in blood. The results suggest that semen could be used to detect PBDE burden in human body as a non-invasive matrix. In addition, the levels of BDE-209 and BDE-153, especially the latter, were much higher in blood than in semen, while the levels of BDE-28, BDE-47 and BDE-99 were comparable in the two matrices, suggesting that low brominated congeners could be more easily transferred to semen than high brominated congeners. Considering different toxicities among the PBDE congeners, it might be more significant to measure PBDEs in semen than in blood for evaluating male reproduction risks of PBDEs.     

Levels of polychlorinated dibenzo-p-dioxins,dibenzofurans (PCDD/Fs) and biphenyls (PCBs) in blood of informal e-waste recycling workers from Agbogbloshie,Ghana, and controls

The formation and environmental release of highly toxic organohalogen compounds associated with informal recycling of waste electric and electronic equipment (e-waste) is a growing problem at e-waste dumps/recycling sites (EWRSs) in many developing countries worldwide. We chose a cross-sectional study design to measure the internal exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) of individuals working on one of the largest EWRSs of Africa, located at Agbogbloshie, Accra, Ghana, and in controls from a suburb of Accra without direct exposure to EWRS activities. In whole blood samples of 21 age matched male exposed individuals (mean age: 24.7 years, SD 6.0) and 21 male controls (mean age: 24.4 years, SD 5.7) 17 PCDD/F congeners were determined. Moreover three indicator PCB congeners (#138, #153 and #180) were measured in blood of 39 exposed (mean age: 27.5 years, SD 11.7) and 19 non-exposed (mean age: 26.8 years, SD 9.7) patients. Besides a health examination, biometric and demographic data, residential and occupational history, occupational exposures and working conditions were recorded using a standardized questionnaire. In the exposed group, median PCDD/F-concentrations were 6.18 pg/g lipid base WHO₂₀₀₅-TEq (range: 2.1–42.7) and significantly higher compared to the control group with 4.60 pg/g lipid base WHO₂₀₀₅-TEq (range: 1.6–11.6). Concentrations were different for 2,3,7,8-TetraCDD, three HexaCDD and all 10 PCDF congeners, indicating a combustion pattern. Using a multivariate regression analysis exposure to EWRS activities was the most important determinant for PCDD/F exposure. Median PCB levels for the indicator congeners #138, #153 and #180 were 0.011, 0.019 and 0.008 μg/l whole blood (ranges: 0.002–0.18, 0.003–0.16, 0.002–0.078) in the exposed group and, surprisingly, significantly higher in the controls (0.037, 0.062 and 0.022; ranges: 0.005–0.46, 0.010–0.46, 0.004–0.21). In a multivariate regression approach e-waste related activities had no positive influence on internal PCB exposure, but rather the time living in Accra. The internal PCB exposure is in particular notable for a country where PCBs have historically never been produced or used. The impact of EWRS activities on organohalogen compound exposure of individuals working at and living in the surroundings of the Agbogbloshie EWRS, and the surprisingly high PCB exposure of people living in Accra not involved in e-waste activities require further investigation.     

Levels of selected persistent organic pollutants in blood from delivering women in seven selected areas of São Paulo State,Brazil

Persistent organic pollutants (POPs) present in the living environment are thought to have detrimental health effects on the population, with pregnant women and the developing foetus being at highest risk. We report on the levels of selected POPs in maternal blood of 155 delivering women residing in seven regions within the São Paulo State, Brazil.The following selected POPs were measured in the maternal whole blood: 12 polychlorinated biphenyls (PCBs) congeners (IUPAC Nos. 99, 101, 118, 138, 153, 156, 163, 170, 180, 183, 187, 194); dichlordiphenyltrichloroethane p,p′-DDT, diphenyldichloroethylene p,p′-DDE and other pesticides such as hexachlorocyclohexanes (α-HCH, β-HCH, γ-HCH), hexachlorobenzene (HCB), chlordane derivatives cis-chlordane, trans-chlordane, oxy-chlordane, cis-nonachlor and trans-nonachlor.Statistical comparisons between regions were performed only on compounds having concentrations above LOD in 70% of the samples. PCB118 congener was found to be highest in the industrial site (mean 4.97 ng/g lipids); PCB138 congener concentration was highest in the Urban 3 site (mean 4.27 ng/g lipids) and congener PCB153 was highest in the industrial and Urban 3 sites with mean concentration of 7.2 ng/g lipids and 5.89 ng/g lipids respectively. Large differences in levels of p,p′-DDE between regions were observed with the Urban 3 and industrial sites having the highest concentrations of 645 ng/g lipids and 417 ng/g lipids, respectively; β-HCH was found to be highest in the Rural 1 site; the γ-HCH in Rural 1 and industrial; the HCB in the Rural 1 and industrial sites and oxy-chlordane and t-NC in the Rural 2 sites. An association between levels of some contaminants and maternal age and parity was also found.