Blood levels of dioxins,furans, dioxin-like PCBs,and TEQs in general populations: A review, 1989–2010

A comprehensive worldwide literature review of blood levels of dioxins and dioxin-like compounds in non-exposed adult general populations was performed. The studies published in 1989–2010 reporting information on polychlorinated dibenzo-para-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho-PCBs (nPCBs), mono-ortho-PCBs (mPCBs) levels and Toxic Equivalencies (TEQs, a summary weighted measure of their combined toxicity) were reviewed. TEQs were calculated using as standard the most recent WHO 2005 reevaluation of Toxic Equivalency Factors (TEFs). Weighted multiple regression analyses adjusted for year, subject's age, type of sample analyzed, method used for values below detection limit, and central tendency measure used were performed for each congener and standardized TEQs (log-transformed). We identified 187 studies regarding 29,687 subjects of 26 countries. Year of blood collection ranged from 1985 to 2008. The studies reporting congener levels 161. In adjusted analyses, European countries showed higher levels of most dioxin-like congeners and TEQs. A strong positive association of subjects' age with most congeners and with TEQ values was found, confirming previous findings. Significant decreases over time (1985–2008) were documented for PCCDs, PCDFs, and TEQs including their contributions. No significant decrease was found for non-ortho-PCBs, notably PCB 126. Only some mono-ortho-PCBs showed clear significant declines. Accordingly, TEQs including only PCB contribution did not decrease over time. In interpreting these findings, it should be considered that for dioxin-like PCBs the analysis period was shorter (17 years), since these compounds were first measured in 1992.     

Dietary exposure to dioxins and PCBs in a large cohort of pregnant women: Results from the Norwegian Mother and Child Cohort Study (MoBa)

Exposure to dioxins and polychlorinated biphenyls (PCBs) during pregnancy and breastfeeding may result in adverse health effects in children. Prenatal exposure is determined by the concentrations of dioxins and PCBs in maternal blood, which reflect the body burden obtained by long term dietary exposure. The aims of this study were (1) to describe dietary exposure and important dietary sources to dioxins and PCBs in a large group of pregnant women and (2) to identify maternal characteristics associated with high dietary exposure to dioxins and PCBs. Dietary exposure to dioxins (sum of toxic equivalents (TEQs) from dioxin-like (dl) compounds) and PCB-153 in 83,524 pregnant women (gestational weeks 17–22) who participated in the Norwegian Mother and Child Cohort Study (MoBa) during the years 2002–2009 was calculated based on a food frequency questionnaire (FFQ) and a database of dioxin and PCB concentrations in Norwegian food. The median (interquartile range, IQR) intake of PCB-153 (marker of ndl-PCBs) was 0.81 (0.77) ng/kg bw/day. For dioxins and dioxin-like PCBs, the median (IQR) intake was 0.56 (0.37) pg TEQ/kg bw/day. Moreover, 2.3% of the participants had intakes exceeding the tolerable weekly intake (TWI) of 14 pg TEQ/kg bw/week. Multiple regression analysis showed that dietary exposure was positively associated with maternal age, maternal education, weight gain during pregnancy, being a student, and alcohol consumption during pregnancy and negatively associated with pre-pregnancy BMI and smoking. A high dietary exposure to PCB-153 or dl-compounds (TEQ) was mainly explained by the consumption of seagull eggs and/or pate with fish liver and roe. Women who according to Norwegian recommendations avoid these food items generally do not have dietary exposure above the tolerable intake of dioxins and dl-PCBs.     

Human exposure to PCDDs, PCDFs and dioxin-like PCBs associated with seafood consumption in Korea from 2005 to 2007

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DLPCBs) were measured in 26 seafoods commonly consumed by the Korean population. The total toxic equivalent (TEQ) concentrations in seafood samples ranged from 0.01 to 6.76 pg TEQ/g wet wt, which were comparable with those found in other countries. The predominant congeners found in seafood samples were 2, 3, 4, 7, 8-PeCDF and 2, 3, 7, 8-TCDF for PCDD/Fs and PCB 118 for DLPCBs. Dietary intakes of PCDD/Fs and DLPCBs from seafood consumption were estimated for various age groups and gender in Korea. The dietary intake of PCDD/Fs and DLPCBs from seafood consumption for the general population was estimated to be 1.23 pg TEQ/kg bw/day, values that are in the range of those reported for other countries. Mackerel, tuna and hairtail contributed to the highest TEQ intakes, which collectively accounted for 66% of the total intake. Among the eight age groups investigated, 3-6 year old children had the highest TEQ exposure, followed by 50-64 years, 30-39 years and <2 years. Considering contributions of seafood consumption to the total dietary intake studies, the dietary TEQ intakes to the general population appear to be below the threshold values by international organizations. The present study may be useful for risk management for dioxins and dioxin-like contaminants in Korean seafood.     

The predictive power of the elimination of dioxin-like pollutants from pigs: an in vivo study

Pigs accidentally given feed contaminated by dioxin-like pollutants are a serious public health issue. We have examined whether pigs with limited exposure during early periods of fattening would be categorized as non-compliant with the EU limit at slaughtering when growth-dilution, excretion and metabolism effects are considered. Sixteen female and sixteen castrated male weaned pigs were divided into four groups (e.g. DG0, DG1, DG2 and DG3) in week 2 after birth. From weeks 3 to 13, groups DG1, DG2, and DG3 pigs were fed with a polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) and polychlorinated biphenyl (PCB) mixture at dosages of 1, 10 and 100 ng-toxic equivalent (TEQ) per kg dry mass feed in capsules, respectively. From weeks 13 to 23, the animals were nourished with clear feed. Control group DG0 was always fed with clear feed. Subcutaneous fat samples were collected at weeks 13, 18 and 23 by biopsies. The pollutant residues were analyzed by high resolution gas chromatography-high resolution mass spectrometry and quantified by a ¹³C-isotope dilution method. The results showed the following: (1) when slaughtered at week 23, the TEQ for DG1 pigs (0.66 ± 0.21 pg/g fat) was under the EU limit of 1 pg PCDD/F-TEQ/g fat; (2) PCDD/F congener-specific first-order elimination rates were linearly correlated with their toxicity equivalency factors (TEFs), and the rates were significantly dose-dependent for the more toxic congeners (TEF ≥ 0.1). Therefore, the pigs' exposure above the EU limit during the early fattening stage did not necessarily lead to their categorization as non-compliant pork; and the residual TEQ for pork can be predicted from early exposure concentrations based on the models established here.     

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.     

Assessment of ecological risk from bioaccumulation of PCDD/Fs and dioxin-like PCBs in a coastal lagoon

The ecological risk posed by dioxin-like PCBs and PCDD/Fs congeners mixtures in five organisms representative of the food web of the lagoon of Venice (Italy) was estimated by applying the US-EPA [US-EPA. Guidelines for Ecological Risk Assessment. EPA/630/R-95/002F. Final Report. U.S. Environmental Protection Agency, Washington, DC; 1998.] procedure. Experimental concentrations of dioxin-like PCBs and PCDD/Fs in sediments, water, and organisms in six lagoon zones were used to define the spatial distribution of the pollutant homolog patterns. The Principal Component Analysis of homolog patterns in biota permitted to remark the difference between PCDD/Fs and dioxin-like PCBs bioaccumulation. Dioxin-like PCBs were found almost unaltered in all selected organisms, while PCDD/Fs homologs underwent an enrichment of low chlorinated furans in fish. The ecological risk for the dioxin-like PCBs and PCDD/Fs was estimated in the selected lagoon zones according to the Hazard Quotient approach by comparing the biota experimental concentrations in TEQ with an Internal No Effect Concentration of the 2,3,7,8-TCDD, estimated from both Ambient Quality Criteria and literature toxicity data. A high potential risk was found for benthic biota (i.e. clam and crab) and for mussel, while a negligible risk was estimated for fish. Moreover, the ecological risk resulted higher in the central part of the lagoon, and lower in the northern lagoon. Finally, the comparison between the TEQ concentrations of each homolog in biota and the estimated ecological risk highlighted that the risk was determined essentially by lower chlorinated PCDD/Fs (i.e. pentachloro and hexachloro PCDD/Fs), and by pentachloro-PCBs. These compounds should be regarded as homologs of concern and preferentially investigated in environmental monitoring of sediment, water, and biota.     

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.     

Evaluation of mixture effects in a crude extract of compost using the CALUX bioassay and HPLC fractionation

Potential synergistic interactions between polycyclic aromatic hydrocarbons in a household sewage sludge compost extract were investigated using the Dioxin-Responsive Chemical-Activated Luciferase gene eXpression (DR-CALUX) assay and reverse-phase high-performance liquid chromatography (RP-HPLC) fractionation. The biological activity of the crude extract was measured in vitro using the CALUX assay. The CALUX activity of the extract was as potent as 360-pg CALUX-TEQ (2,3,7,8-TCDD equivalent value) per g sample, this was 70 times above the WHO-TEQ value which was derived from chemical analyses of dioxins/furans and dioxin-like PCBs of the mixture. The CALUX activity pattern of the crude extract and the retention times of 26 polycyclic aromatic compounds (PACs), as determined by RP-HPLC on an octadecylsilica column, suggested that the dioxin-like compounds with the log K(OW) (n-octanol/water partition coefficient) values corresponding to 6.0-7.0 contributed highly to the whole activity. The CALUX activity of the crude extract was three times the sum of the CALUX activities of the RP-HPLC separated fractions. Mixture effects were assessed by co-exposure of each HPLC fraction and 2,3,7,8-TCDD to the cells. The four concentration levels of added 2,3,7,8-TCDD corresponded to the TEQ value in the original compost sample. The experimental CALUX activity was higher than the predicted CALUX activity for some fractions. It was demonstrated that some compounds in the compost sample interacted synergistically with 2,3,7,8-TCDD in terms of dioxin-like activity. This finding points out the necessity for detailed investigation of synergistic effects in environmental samples.     

Maternal dietary intake of dioxins and polychlorinated biphenyls and birth size in the Norwegian Mother and Child Cohort Study (MoBa)

Maternal diet not only provides essential nutrients to the developing fetus but is also a source of prenatal exposure to environmental contaminants. We investigated the association between dietary intake of dioxins and PCBs during pregnancy and birth size. The study included 50,651 women from the Norwegian Mother and Child Cohort Study (MoBa). Dietary information was collected by FFQs and intake estimates were calculated by combining food consumption and food concentration of dioxins, dioxin-like PCBs and non-dioxin-like PCBs. We used multivariable regression models to estimate the association between dietary intake of dioxins and PCBs and fetal growth. The contribution of fish and seafood intake during pregnancy was 41% for dietary dioxins and dioxin-like PCBs and 49% for dietary non-dioxin-like PCBs. Further stratified analysis by quartiles of seafood intake during pregnancy was conducted. We found an inverse dose–response association between dietary intake of dioxins and PCBs and fetal growth after adjustment for confounders. Newborns of mothers in the upper quartile of dioxin and dioxin-like PCBs intake had 62 g lower birth weight (95% CI: − 73, − 50), 0.26 cm shorter birth length (95% CI: − 0.31, − 0.20) and 0.10 cm shorter head circumference (95% CI: − 0.14, − 0.06) than newborns of mothers in the lowest quartile of intake. Similar negative associations for intake of dioxins and dioxin-like PCBs were found after excluding women with intakes above the tolerable weekly intake (TWI = 14 pg TEQ/kg bw/week). The negative association of dietary dioxins and PCBs with fetal growth was weaker as seafood intake was increasing. No association was found between dietary dioxin and PCB intake and the risk for small-for-gestational age neonate. In conclusion, dietary intakes of dioxins and PCBs during pregnancy were negatively associated with fetal growth, even at intakes below the TWI.     

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.     

Determination of relative assay response factors for toxic chlorinated and brominated dioxins/furans using an enzyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX)

Determination of toxic activity requires knowledge of both the concentration and toxicity to evaluate the risk for adverse human health and environmental effects. A chemically-activated luciferase gene expression cell bioassay system (CALUX) and an antibody-based method enzyme immunoassay (EIA) were used to detect the dioxin-like response of several polybrominated, polychlorinated, and polybrominated/chlorinated dibenzo-p-dioxins/furans (PBDDs/Fs, PCDDs/Fs, and PBCDDs/Fs, respectively). It has been suggested that the biological activity of the brominated and mixed bromo/chloro compounds is similar to their chlorinated analogues (measured by binding to the Ah receptor). PBDD/F, PCDD/F, and PBCDD/F laboratory standards exhibited biological activity ranging over three orders of magnitude. The highest relative potency (REP) values from CALUX analysis, when compared to 2,3,7,8-TCDD, were 2,3,7,8-TBDD at 0.99 (± 0.07), 1,2,3,7,8-PeCDD at 0.69, and 2-Br-3,7,8-TriCDD at 0.72 (± 0.02). Cross-reactivities were calculated using EIA for several PBDDs/Fs and PBCDDs. The highest percent cross-reactivity was found for 2,3,7,8-TBDD at 138 (± 34%), and 2,3,7-TriBDD at 84 (± 36%).     

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.     

Increased risk of non-Hodgkin lymphoma and serum organochlorine concentrations among neighbors of a municipal solid waste incinerator

Organochlorine chemicals may contribute to an increased risk of non-Hodgkin lymphoma (NHL) within non-occupationally exposed populations. Among these chemicals, dioxins and furans were mainly released by municipal solid waste incinerators (MSWIs) until a recent past in France, a source of exposure that is of public concern. We investigated organochlorines and the risk of NHL among neighbors of a French MSWI with high levels of dioxin emissions (Besan?on, France), using serum concentrations to assess exposure. The study area consisted of three electoral wards, containing or surrounding the MSWI. Pesticides, dioxins, furans, and polychlorinated biphenyls (PCBs) were measured in the serum of 34 newly diagnosed NHL cases (2003-2005) and 34 controls. Risks of NHL associated with each lipid-corrected serum concentration were estimated using exact logistic regression. The pesticides β-hexachlorocyclohexane (odds ratio [OR]=1.05, 95% confidence interval [CI]=1.00-1.12, per 10 ng/g lipid) and p,p' dichloro-diphenyl-trichloroethane (DDT) (OR=1.20, 95% CI=1.01-1.45, per 10 ng/g lipid) were associated with NHL risk. Evidence indicated an increased NHL risk associated with cumulative WHO(1998)-toxic equivalency factor (TEQ) concentrations (dioxins, OR=1.12, 95% CI=1.03-1.26; furans, OR=1.16, 95% CI=1.03-1.35; dioxin-like PCBs, OR=1.04, 95% CI=1.00-1.07; and total TEQ, OR=1.04, 95% CI=1.01-1.05), as well as with non dioxin-like PCBs (OR=1.02, 95% CI=1.01-1.05, per 10 ng/g lipid). Most congener-specific associations were statistically significant. This study provides strong and consistent support for an association between serum cumulative WHO(1998)-TEQ concentrations, at levels experienced by people residing in the vicinity of a polluting MSWI, and risk of NHL.     

Evaluation of background persistent organic pollutant levels in human from Taiwan: polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls

This study was intended to determine the background levels of PCDD/PCDFs and PCBs in the Taiwanese population and to investigate factors potentially related to PCDD/PCDF and PCB levels. The levels of seventeen PCDD/PCDFs in the 251 serum samples collected from the general population in Taiwan ranged from 4.92 to 26.7 pg WHO(1998)-TEQ/g lipid (median: 11.5) and those of the twelve dioxin-like PCBs ranged between 1.74 and 21.6 pg WHO(1998)-TEQ/g lipid (median: 6.14). Five factors, age, gender, region of residence, dietary status, and smoking status, showed statistically significant association with the TEQ level of PCDD/PCDFs. The TEQ level of PCBs was statistically associated with age only, but not with the other four factors. The trends observed between age and the levels of PCDD/PCDFs and PCBs were not parallel in young subjects (<30 years old) and old subjects (>30 years old). The levels of PCDD/PCDFs and PCBs increased by 0.16 and 0.03 WHO(1998)-TEQ/g lipid per year for subjects above the age of 30, but there was no evidence of any association between age and the levels for subjects below the age of 30 years. These factors should be considered when investigating relationships between background serum levels of persistent organic pollutants and parameters associated with exposure sources or health outcomes.     

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.     

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.     

Risk assessment of PCDD/Fs levels in human tissues related to major food items based on chemical analyses and micro-EROD assay

Nine groups of food items (freshwater fish, marine fish, pork, chicken, chicken eggs, leafy, non-leafy vegetables, rice and flour) and three types of human samples (human milk, maternal serum and cord serum) were collected for the analysis of PCDD/Fs. Results of chemical analysis revealed PCDD/Fs concentrations (pg g^− 1 fat) in the following ascending order: pork (0.289 pg g^− 1 fat), grass carp (Ctenopharyngodon idellus) (freshwater fish) (0.407), golden thread (Nemipterus virgatus) (marine fish) (0.511), chicken (0.529), mandarin fish (Siniperca kneri) (marine fish) (0.535), chicken egg (0.552), and snubnose pompano (Trachinotus blochii) (marine fish) (1.219). The results of micro-EROD assay showed relatively higher PCDD/Fs levels in fish (2.65 pg g^− 1 fat) when compared with pork (0.47), eggs (0.33), chicken (0.13), flour (0.07), vegetables (0.05 pg g^− 1 wet wt) and rice (0.05). The estimated average daily intake of PCDD/Fs of 3.51 pg EROD-TEQ/kg bw/day was within the range of WHO Tolerable Daily Intake (1–4 pg WHO-TEQ/kg bw/day) and was higher than the Provisional Tolerable Daily Intake (PMTL) (70 pg for dioxins and dioxin-like PCBs) recommended by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) [Joint FAO/WHO Expert Committee on Food Additives (JECFA), Summary and conclusions of the fifty-seventh meeting, JECFA, 2001.]. Nevertheless, the current findings were significantly lower than the TDI (14 pg WHO-TEQ/kg/bw/day) recommended by the Scientific Committee on Food of the Europe Commission [European Scientific Committee on Food (EU SCF), Opinions on the SCF on the risk assessment of dioxins and dioxin-like PCBs in food, 2000.]. However, it should be noted that micro-EROD assay overestimates the PCDD/Fs levels by 2 to 7 folds which may also amplify the PCDD/Fs levels accordingly. Although the levels of PCDD/Fs obtained from micro-EROD assay were much higher than those obtained by chemical analysis by 2 to 7 folds, it provides a cost-effective and rapid screening of dioxin levels in food and human samples.     

Chemical and toxicological characterisation of PBDFs from photolytic decomposition of decaBDE in toluene

A substantial formation of PBDF congeners was observed during photolytic decomposition of decaBDE in toluene. The decaBDE degradation was monitored by chemical and toxicological analysis and in all, twenty-seven mono- to hexasubstituted polybrominated dibenzofurans (PBDFs) were detected in toluene solutions of decabromodiphenyl ether (decaBDE) after irradiation with UV-A, UV-AB and UV-ABC. The concentration levels of PBDFs formed after 16 h of UV exposure increased with wider spectra and were determined to be 3.5, 4.2 and 14 microg/ml after UV-A, UV-AB and UV-ABC irradiation, respectively. In accordance, bioassay derived TEQs (bio-TEQs), determined with the DR-CALUX assay, increased with a similar pattern. The PBDFs formed after the three UV exposures accounted for 0.31%, 0.35% and 1.2% of the initial amount of decaBDE (molar basis). The PBDF congener patterns were consistent in all three UV experiments which imply that no alterations were induced in the PBDF formation or degradation processes due to differences in UV irradiation. However, these processes tended to increase with wider spectra and increasing radiation energy most likely due to the strong absorbance of for example decaBDE at shorter wavelengths. After total decaBDE decomposition the PBDF formation increased significantly in the UV-ABC experiment. The tetra to hexasubstituted BDFs constituted the majority of detected compounds in all experiments. In all samples, the estimated chemical TEQ indicate that the bio-TEQs observed are largely explained by the presence of non-2,3,7,8-substituted PBDFs with relatively low toxicological potencies.     

Uptake of polychlorodibenzo-p-dioxins, polychlorodibenzofurans and coplanar polychlorobiphenyls in chickens

Twelve chickens raised according to commercial standards were fed a diet containing about 30 ng total toxic equivalent (TEQ)/kg for 10 weeks. Persistent pollutants were introduced into the poultry feed via recycled oil to mimic contamination conditions closely resembling those occurring during the Belgian crisis five years ago. Absorption of congeners with the same chlorination degree did not seem to depend on the substitution, demonstrating that unlike for cows, no preferential absorption for 2,3,7,8-substituted compounds could be remarked for chickens. As already observed, absorption decreased with increasing number of chlorines and was not linearly dependent on the octanol/water partition coefficient. On the other hand, no real differences were observed in the absorption of coplanar polychlorinated biphenyls (c-PCBs) with regard to degree of chlorination. When monitored during the course of experiment, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and c-PCBs in excreta reached an apparent steady state after 5 weeks. Only 2,3,7,8-substituted dioxins or furans were found in tissues and eggs. All organs showed the same congener profile and similar lipid-normalized concentration, except for the liver. Bioconcentration factors were evaluated, highlighting that the liver preferentially retained highly chlorinated congeners. No depletion of dioxin and PCB concentration was observed after 8 and 14 weeks of control diet, but high inter-individual variation occurs.     

Emission factors for PCDD/PCDF and dl-PCB from open burning of biomass

The Stockholm Convention on Persistent Organic Pollutants includes in its aims the minimisation of unintentional releases of polychlorinated dibenzo-dioxins and dibenzofurans (PCDD/PCDF) and dioxin like PCB (dl-PCB) to the environment. Development and implementation of policies to achieve this aim require accurate national inventories of releases of PCDD/PCDF/dl-PCB. To support this objective, the Conference of Parties established a process to review and update the UNEP Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. An assessment of all emission inventories was that for many countries open burning of biomass and waste was identified as the major source of PCDD/PCDF releases. However, the experimental data underpinning the release estimates used were limited in number and, consequently, confidence in the accuracy of the emissions predictions was low. There has been significant progress in measurement technology since the last edition of the Toolkit in 2005. In this paper we reassess published emission factors for release of PCDD/PCDF and dl-PCB to land and air.In total, four types of biomass and 111 emission factors were assessed. It was found that there are no systematic differences in emission factors apparent between biomass types or fire classes. The data set is best described by a lognormal distribution. The geometric mean emission factors (EFs) for releases of PCDD/PCDF to air for the four biomass classes used in the Toolkit (sugarcane, cereal crops, forest and savannah/grass) are 1.6 μg TEQ (t fuel)⁻¹, 0.49 μg TEQ (t fuel)⁻¹, 1.0 μg TEQ (t fuel)⁻¹ and 0.4 μg TEQ (t fuel)⁻¹, respectively. Corresponding EFs for release of PCDD/PCDF to land are 3.0 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹ and 0.67 ng TEQ (kg ash)⁻¹. There are now also sufficient published data available to evaluate EFs for dl-PCB release to air for sugarcane, forest and grass/savannah; these are 0.03 μg TEQ (t fuel)⁻¹, 0.09 μg TEQ (t fuel)⁻¹ and 0.01 μg TEQ (t fuel)⁻¹, respectively. The average EF for dl-PCB release to land is 0.19 ng TEQ (kg ash)⁻¹. Application of these EFs to national emissions of PCDD/PCDF for global estimates from open burning will lower previous estimates of PCDD/PCDF releases to air and to land by 85% and 90%, respectively. For some countries, the ranking of their major sources will be changed and open burning of biomass will become less significant than previously concluded.