Levels of PCDDs, PCDFs and dioxin-like PCBs in raw cow's milk collected in France in 2006

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) are widespread environmental contaminants. A French national survey was carried out in April 2006 to assess the concentrations of PCDD/Fs and dioxin-like PCBs (DL-PCBs) in raw cow's milk. A random sampling scheme stratified by region was applied to collect 239 raw milk samples from 93 plants belonging to 17 dairy companies. Compared to a previous survey led in 1998 analyzing half-skimmed drinking milk in France, the PCDD/Fs level was cut by half, with an average concentration of 0.33 pg toxic equivalent (TEQ)/g fat in 2006. The mean DL-PCBs concentration was 0.57 pg TEQ/g fat and subsequently the sum of PCDD/Fs and DL-PCBs was 0.90 pg/g fat, values below the thresholds defined by the European Union regulations.     

Longitudinal increases in PCDD/F and dl-PCB concentrations in human milk in northern China

There is a dearth of information on the temporal changes in polychlorinated dibenzodioxin/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) contamination, in both environmental and biological specimens, in China. We compared the concentrations of PCDD/Fs and dl-PCBs in human milk collected in Shijiazhuang, Hebei Province, in northern China in 2002 (n=30) and 2007 (n=20). The level of PCDD/Fs and dl-PCBs showed an increasing trend. The mean concentrations of PCDD/Fs plus dl-PCBs were 4.47 TEQ pg g(-1) fat and 6.24 TEQ pg g(-1) fat in human milk from Shijiazhuang in 2002 and in 2007, respectively. Based on statistical analysis of questionnaire data collected by in-person interviews with mothers, we found positive correlations between consumption of sea fish and PCDFs. The PCDDs, PCDFs, PCDD/Fs, and PCDD/Fs plus dl-PCBs levels in individuals consuming greater amounts of sea fish were higher than those consuming less sea fish, both with and without adjustments for potential confounding factors. Among 17 congeners of PCDD/Fs, the 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF congener concentrations in 2007 increased 134%, 55%, 53%, 57%, 65% and 130% when compared to 2002 levels, respectively. The 2007 dl-PCB congener levels were greater than those of the 2002 samples, with the exception of PCB81 and PCB77. Specifically, PCB105, PCB114, PCB118, PCB123 and PCB156 had increased greater than twofold from 2002 to 2007. Continuous surveillance of PCDD/F and dl-PCB levels in human milk is needed to accurately evaluate both environmental contamination and the human health risk to neonates in China.     

PCDD/Fs and PCBs in butter samples from new European Union member states and a candidate country: analytical quality control, results and certain PCB-specific aspects

Milk and milk products have shown to be good indicator samples for the contamination of persistent organic pollutants (POPs) along the food chain. To gather information on whether exposure to dioxins and PCBs might cause a problem in countries about to join the European Union in 2004 or later, a study for evaluation of dioxin and levels of PCBs in 16 butter samples from eight countries (Cyprus, Czech Republic, Estonia, Lithuania, Poland, Romania, Slovenia and Slovakia) was performed. Comprehensive quality assurance/quality control (QA/QC) was requested. For this, eight quality control samples were included (in comparison to long-term mean, mean recovery for WHO-PCDD/F-TEQ of 97.9% with a CV of 3.0%, mean recovery for WHO-PCB-TEQ of 100.4% with a CV of 3.3%). Additionally, all butter samples were run as duplicates resulting in a confidence region of 95% statistical certainty of 4.6% for WHO-PCDD/F-TEQ and of 3.5% for WHO-PCB-TEQ. All samples except one from Romania were in the range of 0.21-0.59 pg WHO-PCDD/F-TEQ/g fat (upper bound), all samples except one from Romania and one from Estonia in the range of 0.32-0.82 pg WHO-PCB-TEQ/g fat (upper bound) and all samples except one from Romania and one from Estonia in the range of 0.57-1.23 pg sum WHO-TEQ/g fat (upper bound). The maximum values were found in samples from Romania (0.98 pg WHO-PCDD/F-TEQ/g fat; 1.75 pg WHO-PCB-TEQ/g fat) and Estonia (0.26 pg WHO-PCDD/F-TEQ/g fat; 1.62 pg WHO-PCB-TEQ/g fat). As a conclusion, all samples except one from Romania and one from Estonia were in the range of the actual low background contamination for PCDD/F and dioxin-like PCBs. The samples with elevated concentrations were below the EU action and maximum levels which have been valid since 2002, or will be applied from November 2006. In all samples except in one from Estonia, the contribution of dioxin-like PCBs to sum WHO-TEQ was 47-68% which reflects the usual range in Europe. In one sample from Estonia this contribution was 86% which points to a particular yet unknown PCB source. Thirty eight PCB congeners were determined allowing a detailed discussion of the relative contribution of individual congeners to the total PCB concentration. Correlation between PCB 153 and WHO-PCB-TEQ varied considerably between samples from different countries. Major tetra- or pentachlorinated mono-ortho PCBs without assigned TEFs were PCBs 60, 66, 74, and 110.     

Dietary intake of PCDDs, PCDFs and dioxin-like PCBs, due to the consumption of various marine organisms from Korea

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) residues were measured in 70 marine organisms (40 species) from Korean coastal waters. The PCDD/Fs residues in the organisms varied from 0.02 to 4.39 pg WHO-TEQ/g wet weight and the DL-PCBs residues varied from 0.008 to 6.0 pg WHO-TEQ/g wet weight. The levels in fish from Korean coastal waters were comparable to those found in other countries. Comparing organism groups, the highest PCDD/Fs and DL-PCBs residues were recorded in crustaceans, followed by fish, cephalopods, bivalves and gastropods. Although the congener distributions of PCDD/Fs and DL-PCBs in the organism groups were different, the dominant contributors to the total TEQ concentrations in all groups were 2,3,4,7,8-pentachlorinated dibenzofuran (PeCDF), 1,2,3,7,8-pentachlorinated dibenzo-p-dioxin (PeCDD) and PCB 126. The dietary intake of PCDD/Fs and DL-PCBs from the consumption of marine organisms in Korea was estimated to be 0.68 pg WHO-TEQ/kg bodyweight/day. The contribution of DL-PCBs to the total dietary intake from all organisms groups averaged 60%. The relative contribution of each organism group to the total dietary intake was, in descending order: fish, crustaceans, cephalopods, bivalves and gastropods. The current dietary intake was lower than those in countries with a similar dietary pattern to Korea, but higher than those in countries with smaller quantities of seafood consumption.     

Feeding trial on rainbow trout: comparison of dry fish feed and Baltic herring as a source of PCDD/Fs and PCBs

Fish is an important source of dietary intake of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). To assess bioaccumulation of PCDD/Fs and PCBs in farm-raised fish, rainbow trout were fed with either Baltic herring or dry fish feed. Baltic herring feed had a PCDD/F sum concentration of 125 ng kg(-1) dry weight (d.w.), and dry fish feed contained 18.2 ng kg(-1) d.w. of PCDD/Fs. The PCB concentrations of Baltic herring and dry fish feed were 188 and 48.7 microg kg(-1) d.w., respectively. After feeding with Baltic herring for 4 months, the PCDD/F concentration of the rainbow trout fillet was 27.3 ng kg(-1) fresh weight (f.w.), which was 7.0-fold higher than the initial concentration. The PCDD/F concentration and congener profile in rainbow trout had become almost the same as in Baltic herring. PCDD/Fs were accumulated in the fillet with an efficiency of 21%. Feeding of rainbow trout with dry fish feed resulted in a PCDD/F concentration of 8.08 ng kg(-1) f.w., denoting a 2.1-fold increase from the initial level. The accumulation efficiency was 29%. Time trends in PCB concentrations followed those of PCDD/Fs. After 4 months, the PCB sum concentration in herring-fed rainbow trout was 94.4 pg kg(-1) f.w., whereas in dry fish feed-fed rainbow trout it was 38.6 microg kg(-1) f.w. Accumulation efficiencies of PCBs were higher than those of PCDD/Fs. Based on the accumulated PCDD/F and PCB concentrations, it was estimated that frequent consumption of rainbow trout fed with Baltic herring could lead to a human daily intake that exceeds the recommendation of WHO.     

A survey of PCB congeners in U.K. cows'' milk

Samples of unpasteurised bulked milk, taken directly from ten herds of dairy cattle on rural and urban farms in the north west of England on five separate sampling occasions, were analysed for a range of PCB congeners. ΣPCB concentrations (sum of 37 congeners) ranged from 3.4–16.4 ng/g milk fat with a mean ΣPCB concentration of 8.4 ng/g milk fat. The dominating congeners were 118, 153, 138 and 180, which contributed 15%, 20%, 17% and 9% of the ΣPCB load respectively. The chlorine pattern of the congeners which made moderate or major contributions to the ΣPCB concentration were typically substituted at both para positions (4, 4′), while the PCB congeners not detected in the milk had at least one ring that was not 4-substituted. These results indicate the 4,4′ substitution pattern as being the key to PCB persistence in cows. It is estimated that consumption of typical daily intakes of milk with the PCB concentrations measured in this study would contribute 11 % of the average daily ΣPCB intake for individuals in the UK. This contribution would increase to 30% when exposure through the consumption of dairy products prepared from such milk (e.g. cheese, butter) is taken into account. It is estimated that the inclusion of the TEF assigned PCBs would typically increase the TEQ rating of cows' milk by approximately 40% over that attributed to PCDD/Fs alone.     

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France)

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). summation operator2,3,7,8-PCDD/F and summation operator7ICES PCB air concentrations (0.2-1.4 and 31-57pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476fg L(-1)) and low for PCBs (138-708pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33ng g(-1) d.w., respectively) and mussel (13-21pg g(-1) d.w. and 10-39ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.     

PCDD/Fs and DL-PCBs in feeding fats obtained as co-products or by-products derived from the food chain

Among the tasks included in the "Quality and safety of feeding fats obtained from co-products or by-products of the food chain" Project, supported by the European Union and included in the 6th Framework Program, a number of fats and oils collected as co- or by-products from the food chain were selected for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (DL-PCBs). In the majority of the cases these samples are currently employed as feed ingredients. Nevertheless, additional fats, which are forbidden for feedstuff purposes were also considered in this study. In general terms, fats and oils were classified taking into account their nature and the processes applied to obtain these co- or by-products. PCDD/F and DL-PCB levels were evaluated in a first group of samples composed of fish oils, animal fats and lecithins. As expected, fats and oils with an animal origin presented higher concentrations, expressed in pg WHO-TEQ/g, compared to the levels found in vegetable samples like lecithins. The category of fish oils had the highest values for both PCDD/Fs and the sum of PCDD/Fs and DL-PCBs, with some samples showing levels above the maximum established at the present legislation related to the presence of PCDD/Fs and DL-PCBs in animal feed [Commission Directive 2006/13/EC of 3 February 2006 amending Annexes I and II to Directive 2002/32/EC of the European Parliament and of the Council on undesirable substances in animal feed as regards dioxins and dioxin-like PCBs. Official Journal of the European Communities L32, 44-53]. In a second group, fats and oils with a more complex composition obtained from different transformation processes or even mixtures of fats were considered; thus, acid oils from chemical refining, acid oils from physical refining, recycled cooking oils, oils extracted from exhausted bleaching earths, hydrogenated by-products, fatty acids calcium soaps and miscellaneous fats were analyzed. The data revealed a significant variability in PCDD/F and DL-PCB levels, expressed in pg WHO-TEQ/g, in these products. It has to be pointed out that the analyses of fats and oils belonging to these categories of products were sometimes difficult due to the complexity of the samples. In terms of legislation most of these samples cannot be easily included into one of the specific categories of substances intended for feedstuff purposes that are regulated in Commission Directive 2006/13/EC.     

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho substituted biphenyls in polar bear milk from Svalbard (Norway)

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g⁻¹ fat (0.2–1.6 pg ml⁻¹ milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.     

Dietary exposure to polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls of the French population: Results of the second French Total Diet Study

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) bioaccumulate through the food chain and are therefore of public health concern. Exposure to these compounds was assessed in the second French Total Diet Study (TDS). Food samples (n=583) were collected to be representative of the whole diet of the population, prepared as consumed, and analyzed. Contamination data were combined with national individual food consumption data. Mean exposure (95th percentile) to PCDD/F+DL-PCBs was assessed to be 0.57 (1.29) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the adult population and 0.89 (2.02) pg TEQ(WHO-98) (kg bw)(-1) d(-1) in the child and teenager population. Less than 4% of the population exceeded the health-based guidance value for PCDD/F+DL-PCBs. Mean exposure (95th percentile) to the six indicator PCBs (PCB 28, 52, 101, 138, 153, 180) was estimated at 2.71 (7.90) ng (kg bw)(-1) d(-1) in the adult population and 3.77 (11.7) ng (kg bw)(-1) d(-1) in the child and teenager population. Only 2.6% of the adults [CI(95%): 1.9; 3.3] and 6.5% of the children and teenagers [5.2; 7.8] exceeded the health-based guidance value for total PCBs. These results show that the contamination levels in food and therefore the exposure of the general French population to PCDD/Fs and PCBs have declined (by a factor of 3.2 for PCDD/F+DL-PCBs and about three for total PCBs) since the last evaluation, which was conducted using another methodology in 2005 and 2007, and show the efficiency of the European risk management measures which came into force after these evaluations.     

Occurrence of PCBs, PCDD/Fs, PBDEs and DDTs in Spanish breast milk: enantiomeric fraction of chiral PCBs

Concentrations and congener specific profile of DDTs, PCBs and PCDD/Fs have been determined in a number of Spanish breast milk samples. The concentrations found indicate a decreasing tendency compared to previous data from the 1990s. Mean concentrations of 238 ng/g fat weight, 111 ng/g fat weight and 82.1 pg/g fat weight were found for DDTs, PCBs and 2,3,7,8-PCDD/Fs, respectively. When the WHO-TEQs were calculated, PCDD/Fs was the family contributing with the highest percentage to the total (62-84%), followed by the non-ortho PCBs (10-25%) and the mono-ortho PCBs (5-24%). The congener specific accumulation patterns found were comparable to those reported in other studies in industrialised countries. In addition, the levels of 9 PBDEs congeners have been also determined in the breast milk samples. The concentrations ranged from 0.04 to 1.38 ng/g fat weight. The enantiomeric enrichment of a number of chiral PCBs in the breast milk samples, including congeners 84, 91, 95, 132, 135, 149, 171, 174, 176 and 183, has also been studied, for some of them for the first time in this matrix.     

Survey of commercial pasteurised cows' milk in Wallonia (Belgium) for the occurrence of polychlorinated dibenzo-p-dioxins,dibenzofurans and coplanar polychlorinated biphenyls

Congener-specific analyses of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 4 non-ortho (coplanar) polychlorinated biphenyls (cPCBs) were performed on 35 samples of commercial long-life pasteurised cows' milk issued from eight different brands available in Walloon supermarkets (Belgium). The observed congener profile was characteristic of milk samples issued from industrialised countries with good inter and intra-brand reproducibility's. The PCDDs to PCDFs ratio was equal to 1.8 in concentration. The toxic equivalent (TEQ based on WHO-TEF) value for PCDD/Fs in all analysed milks was 1.09+/-0.30 pg TEQ/g fat (range 0.86-1.59), which is below the recommended EU non-commercialisation threshold value of 3 pg TEQ PCDD/Fs/g of milk fat. The mean TEQ value including cPCBs was 2.23+/-0.55 pg TEQ/g fat. These PCBs actually contributed for 49+/-8.6% of the total TEQ. Among PCDD/Fs and cPCBs, tetrachloro dibenzo-p-dioxin (TCDD), pentachloro dibenzo-p-dioxin (PeCDD), pentachloro dibenzofurans (PeCDFs) and 3,3',4,4',5-pentachloro biphenyl (PCB-126) were the most important contributors to the TEQ. Estimated daily intake (EDI) due to consumption of such milks was 0.34 pg TEQ/kg of body weight/day for PCDD/Fs and 0.69 pg TEQ/kg of body weight/day when cPCBs were included.     

Screening of human health risk to infants associated with the polychlorinated biphenyl (PCB) levels in human milk from Punjab Province,Pakistan

This study assessed the polychlorinated biphenyl (PCB) levels in human milk and its associated health risk to infants from rural and urban settings of five districts of Punjab Province, Pakistan. The ∑₃₄PCB concentrations ranged from 30.9 to 68.3 ng g^?1 on lipid weight (l.w.) basis. The ∑₈DL-PCB concentrations were ranged from 0.29 to 1.35 ng g^?1 l.w., (mean 6.2 ± 8.7 ng g^?1 l.w.), with toxicity equivalent to polychlorinated dibenzodioxins (PCDDs) ranging from 8.58 × 10^?6 to 0.05 ng TEQ g^?1 l.w. The spatial trend of PCB levels in human milk revealed higher bioaccumulative levels for urban mothers as compared with rural counterparts. The estimated daily intake (EDI) values of DL-PCBs to infants through trans-mammary transfer were considerably higher than tolerable daily intake limits established by WHO (i.e., 1–4 pg TEQ kg^?1 bw) and other globally recognized organizations. Similarly, the hazard quotient values for TEQ ∑₈DL-PCBs (range 1.21 to 79.87) were far above the benchmark value of 1 at all the sampling sites, indicating the high levels of adverse health risks to infants in the region through breast milk consumption. The ∑₃₄PCB levels were found to be negatively correlated with mother’ age (r = ?0.31; p = 0.02), parity (r = ? 0.85; p = 0.001), and infant’ birth weight (r = ? 0.73; p = 0.01). The present study suggests undertaking comprehensive public health risk assessment studies and firm regulatory measures to safeguard human health risks.

     

Polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls levels in human breast milk from different regions of Turkey

Human breast milk offers the optimal nutrition for all infants and have been widely used in biomonitoring programs to assess human exposure to lipophylic environmental contaminants such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB). There are no previous reports from Turkey on chemically determined levels of PCDDs, PCDFs, and PCBs in human breast milk expressed as World Health Organization (WHO) toxic equivalents (TEQ). To get an overview of the levels of these contaminants in Turkish human milk, samples from 51 Turkish women living in the Ankara, İstanbul, Antalya, Kahramanmaraş, and Afyon provinces were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) throughout 2007. The mean concentrations of WHO_PCDD/F-TEQ and WHO_PCB-TEQ of all samples from the five regions were 7.5 and 3.1 pg g⁻¹ on a lipid basis, respectively. PCDD/F concentrations ranged between 0.78 and 29.3 pg WHO-TEQ g⁻¹ fat (1.7 and 36.2 pg WHO-TEQ g⁻¹ fat, respectively, including PCB). Of the five studied locations, the lowest levels of ∑TEQs (PCDD/F + PCB) were found in the Afyon (6.8 pg WHO-TEQ g⁻¹ fat) and the highest in the Antalya (15.6 pg WHO-TEQ g⁻¹ fat) province. The results have been discussed in terms of regions and PCDD/F and PCBs for which analyses had been made. The mean levels of PCDD/Fs and PCBs in Turkish human milk are comparable to that found in other countries.     

Levels of PCDD/Fs and DL-PCBs in selected foods and estimated dietary intake for the local residents of Luqiao and Yuhang in Zhejiang, China

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured by high resolution gas chromatograph/high resolution mass spectrometer (HRGC/HRMS) in six food groups from Luqiao (LQ) where the e-waste has been recycled and from Yuhang (YH) where the agriculture dominates in Zhejiang Province in China. The total WHO-TEQ values of PCDD/Fs and DL-PCBs in selected foods from LQ were significantly much higher than those from YH. The highest level of the total WHO-TEQ was in crucian carp (10.87 pg g(-1) w.w.) followed by duck (3.77 pg g(-1) w.w.), hen eggs (2.80 pg g(-1) w.w.), chicken (2.43 pg g(-1) w.w.), rice (0.08 pg g(-1) w.w.) and vegetables (0.022 pg g(-1) w.w.) in LQ. By contrast, the highest levels were measured in duck (0.74 pg g(-1) w.w.) followed by hen eggs (0.69 pg g(-1) w.w.), crucian carp (0.55 pg g(-1) w.w.), chicken (0.44 pg g(-1) w.w.), vegetables (0.002 pg g(-1) w.w.) and rice (0.0002 pg g(-1) w.w.) in YH, respectively. The monthly intake of PCDD/Fs and DL-PCBs for the local residents was 401.75 pg WHO-TEQ g(-1) w.w. in LQ, which is above the provisional tolerable monthly intake (PTMI) set by the Joint FAO/WHO Expert Committee on Food Additives (JECFA). We determined a monthly intake of 37.13 pg WHO-TEQ g(-1)w.w. in YH, which is below the PTMI. Crucian carp was the predominant contributor to the estimated monthly intake (EMI), accounting for 67.74% and 36.51% in LQ and YH, respectively. High levels of PCDD/Fs and DL-PCBs in selected foods indicate severe contamination of these pollutants in the e-waste recycling site.     

Concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk of women from Catalonia, Spain

In this study, the concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain, were determined. The study was performed after 4 years of regular operations in the facility and the present PCB levels were compared with baseline concentrations obtained in a pre-operational program. PCBs and PBDEs levels were determined by HRGC/HRMS in 15 samples. In the present study planar PCBs ranged from 1.3 to 6.3 pg WHO-TEQ/g fat with a mean value of 3.8 pg WHO-TEQ/g fat. After adding dioxin-like mono-ortho-PCBs the total PCB-TEQ concentrations ranged from 3.8 to 13.3 pg WHO-TEQ/g fat (mean value: 8.7 pg WHO-TEQ/g fat). A comparison of the current data with those obtained in the baseline study showed significant decreases for both planar and total WHO-TEQ of PCBs: 47.9% and 44.6%, respectively. PCB concentrations in milk of women living in urban zones were higher than those living near industrial areas (10.1 and 7.4 pg WHO-TEQ/g fat, respectively). Mean PBDE concentrations were 2.2 and 2.5 ng/g fat for women living in urban and industrial zones, respectively. Dietary intake of PCBs and PBDEs for a standard adult woman samples were 898 and 843 ng/day for PCBs, and 72 and 63 ng/day for PBDEs, for residents in urban and industrials areas, respectively. This study suggests that dietary intake is more relevant for human exposure to PCBs and PBDEs than living near the HWI.     

Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

PCDD/Fs and PCBs in Baltic herring during the 1990s

Baltic herring samples caught from the Baltic Sea during the spring periods of 1993-1994 and 1999 were analysed for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB). For analyses, 1570 individual herring were combined to 120 pools. Correlations between concentrations of congeners 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF, and age of herring were the strongest (r>0.8) followed by correlations between PCB congeners PCB 105, 118, 126, 156, 169 and 180 (r>0.7), and age of herring. Due to higher fat percentage in herring in the Gulf of Bothnia the concentrations of PCDD/Fs and PCBs on fresh weight (fw) basis were higher than in herring in the Gulf of Finland. The concentrations of WHO(PCDD/F)-TEQs ranged from 1 to 27 pg/g fw, depending on the age and catchment area of herring, and concentrations of WHO(PCB)-TEQs reached 32 pg/g fw. Between the two studied time points no clear downward trend in concentrations was observed.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans and 'dioxin-like' PCBs in flue gas emissions from municipal waste management plants

The aim of this work is to give representative data on polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyl (PCBs) from stack gas emissions of an urban solid waste management plant which has to comply with the limit of 0.1 ng I-TEQ/Nm3. In particular, the study is focused on 29 target compounds, the seventeen 2,3,7,8-PCDDs/Fs, four non-ortho PCBs and eight mono-ortho PCBs which configure so-called 'dioxin-like' PCBs (DL-PCBs). To this end, emission measurements were performed during one year over the three operating combustion lines in a selected waste management plant. In general, accurate methodology allowed characterizing all target compounds in almost all the samples analyzed. In addition, a typical pattern for DL-PCBs is reported. The pattern presented PCB #118 to be the highest, nevertheless the figures demonstrated DL-PCBs contribution to the total TEQ around 3% being PCB #126 the most important congener due to its TEF of 0.1. Finally, remarkable differences were achieved in comparison with both environmental and biological samples such as soils, sediments, human milk or fish since these matrices may present DL-PCB contribution to the total TEQ up to 77%.     

Increase of the PCDD/F-contamination of milk, butter and meat samples by use of contaminated citrus pulp

In Germany from 1993 to 1997, the polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) contamination of food decreased slowly but constantly. However, for milk and butter, this trend was gradually reversed beginning in September 1997: From summer 1997 to February 1998 the average PCDD/F contamination of dairy products increased from a low level of about 0.6 pg I-TEQ/g fat in summer 1997. The dioxin content, of a limited number of randomly collected samples, rose on average to 1.41 pg I-TEQ/g fat (median 1.06 pg I-TEQ/g fat) in different regions of Germany in February 1998. A butter sample from the Netherlands with 1.96 pg I-TEQ/g fat hinted at the same source. The congener pattern in all contaminated milk and butter samples had elevated amounts of 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD. Also, meat samples (beef, cow's meat and veal) with the same dioxin pattern were found to contain between 1.72 and 4.26 pg I-TEQ/g fat (background contamination of 0.53 pg I-TEQ/g fat). Large number of samples were analyzed to find a key for the cause. With a farmer producing milk with about 4.9 pg I-TEQ/g fat, a new source of PCDD/F for food contamination was discovered: the use of PCDD/F contaminated citrus pulp from Brazil as feed material for ruminants on a very large scale. Containing about 5-10 ng I-TEQ/kg, this component was about 20-100 times more highly contaminated than average feed with background contamination. Very complex pieces of circumstantial evidence were gathered to prove the correlation between this component of feed and the increase of dioxin contamination in milk. With respect to the huge trade of this feed ingredient on the global market, many other countries were involved. As an immediate response on these findings, the European Community fixed a preliminary maximum permitted level of 500 pg I-TEQ/kg citrus pulp, valid since August 1998.