Distribution of polybrominated diphenyl ethers (PBDEs) and other persistent organic pollutants in human serum from Greece

Human serum samples (n=61) were collected in Attika, Greece between June and October 2007 and analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Thirty samples were collected from computer clerks of a large computer company in Athens working full-time with computers, and thirty-one from a control population in the Attika region with no computer use. Σ(5)PBDE concentrations (sum of tri- to hexa-BDEs) in all samples (n=61) ranged from 0.68 to 13.3 ng g(-1) lipid, with a median of 1.07 ng g(-1) lipid. These concentrations are on the lower end of those reported from other countries, probably reflecting lower usage of PBDE-containing products or lower exposures to these chemicals. Individual and Σ(5)PBDE concentrations did not statistically differ between the two groups of computer clerks and non-computer users (p>0.05), with the exception of BDE 153 (p=0.033). The predominant congener was BDE 153, followed by BDEs 47, 100, 99, 183, 154 and 28. HBCD was also detected in 70% of the samples. BDE 209 was detected in 8 out 61 samples (13%), with concentrations ranging from 1.18 to 19.1 ng g(-1) lipid, and a median of 2.94 ng g(-1) lipid. No age dependency was found for PBDEs. Σ(11)PCB (sum of PCBs 74, 99, 118, 138, 146, 153, 156, 170, 180, 183 and 187,) in all samples (n=61) ranged from 36 to 402 ng g(-1) lipid, with a median of 110 ng g(-1) lipid. pp'-DDE concentrations ranged from 53.8 to 1649 ng g(-1) lipid, with a median of 268 ng g(-1) lipid. This is the first study to report levels of PBDEs in a possibly occupationally exposed subset of the Greek population.     

Brominated flame retardants and other organochlorine pollutants in human adipose tissue samples from the Czech Republic

Brominated flame retardants (BFRs) represented by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) together with major persistent organochlorine pollutants, polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs), were determined in adipose tissue samples (n=98) obtained by liposuction of Czech subjects. Compared to other organochlorine pollutants (mostly PCBs and DDTs), levels of PBDE were lower by 2 orders of magnitude ranging from 0.2 to 54.3 ng/g lipid weight. PBDE congeners No. 47, 99, 153 and 183 were the most abundant constituting up to 90% of these pollutants in adipose tissue. The PBDEs content measured in this study was comparable with data reported in similar samples collected in Spain, Sweden, Belgium and Japan, whilst slightly lower than in the United States. Regarding PCBs, the dominating congeners were No. 138, 153 and 180 representing up to 90% of indicator congeners. The levels of PCBs were similar to those found in other European countries. While no age dependency was found for PBDEs, an increase of PCB and OCP levels with age was observed. Different exposure routes of donors were documented by the absence of the relationship between PCBs and OCPs.     

Polychlorinated biphenyl levels in adipose tissue of primiparous women in Turkey

Polychlorinated biphenyls (PCBs) are a mixture of 209 possible congeners with different chlorine substitutions and they are potentially hazardous compounds in the environment for human beings. The high lipophilicity and the resistance to biodegradation of PCBs allow the bioaccumulation of these chemicals in the fatty tissues of organisms. The objective of this study was to determine the levels of PCBs in the adipose tissue of women living in Ankara, Turkey. For this purpose, levels of seven major persistent PCB congeners (IUPAC Numbers: 28, 52, 101, 118, 138, 153, 180) were measured in 29 primiparous mothers' adipose tissue samples by gas chromatography with electron capture detection (GC-ECD). PCB IUPAC numbers 138, 153 and 180 were the most abundant congeners, each accounting for > 20% of the total PCB content of adipose tissue. PCB 153 was the dominant congener in all the samples (141.7 +/- 132.3 ng/g lipid wt. basis). The results are compared with the similar studies from other countries. The concentrations of PCB 28, PCB 52 and PCB 101 were found to be higher than those found in industrialized countries. This study is important in terms of being the first study of determination of PCB levels in adipose tissue samples in Turkey.     

Organochlorine levels in edible fish from the Marmara Sea, Turkey

Samples of 12 edible fish species from the Marmara Sea were analyzed for organochlorines (PCBs, DDTs, HCB, HCHs, toxaphene, etc.). The results showed that the total concentrations ranged from 329.41 ng/g fat to 1453.87 ng/g fat. DDT group components made up almost half or more of organochlorine contamination. Levels in red mullet were compared with those from neighbor seas. The sum of DDTs as well as HCHs concentrations were markedly lower than in the Black Sea but higher in the Aegean Sea and Mediterranean. Thus, inflow from the Black Sea might be considered as a contamination source for DDT and HCH contamination. On the other hand, total PCB concentration (sum of congeners 28, 52, 101, 118, 138, 153 and 180) detected in this study was comparable or lower than those from the Aegean Sea and Mediterranean. Toxaphene was a minor contaminant. Measured values were below maximum residue levels for human consumption.     

Maternal transfer of organochlorines and brominated flame retardants in blue tits (Cyanistes caeruleus)

Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits (Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p,p'-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623+/-148 ng/g lipid weight (lw) to 1040+/-47 ng/g lw for the sum PCBs, from 342+/-24 ng/g lw to 235+/-17 ng/g lw for the sum OCPs and from 49+/-5 ng/g lw to 27+/-5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for sum PCBs, sum OCPs and sum PBDEs decreased significantly from 1.0+/-0.09 to 0.7+/-0.003, 1.1+/-0.1 to 0.7+/-0.02 and 1.2+/-0.14 to 0.8+/-0.05, respectively, during the course of egg laying. The profiles of the females and eggs differed significantly for the PCBs, OCPs and PBDEs. There was a higher contribution of lower chlorinated PCB congeners (CB 28, CB 52, CB 95, CB 101 and CB 110), BDE 183, p,p'-DDT and other less persistent OCPs in the females compared to their eggs. Maternal transfer in blue tits seemed to be selective for the more bioaccumulative and persistent congeners/compounds.     

Levels of organohalogenated persistent pollutants in human milk from Kahramanmaraş region, Turkey

The levels of 1,1,1-trichloro-bis-2,2'-(4-chlorophenyl) ethane (p,p'-DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers (HCHs), chlordanes (trans- and cis-chlordane, oxychlordane and trans-nonachlor), 11 polychlorinated biphenyl (PCB) congeners, and 7 polybrominated diphenyl ether (PBDE) congeners were measured in 37 individual human milk samples from Kahramanmara? region, Turkey. Organochlorine pesticides were the major contaminants in the milk samples. p,p'-DDE and p,p'-DDT were detected in all samples, while beta-HCH had a detection frequency of 97%. The sum of the DDTs in human milk samples varied between 0.52 and 315.8 ng/g wet weight (ww) with a mean ratio between p,p'-DDE and p,p'-DDT equal to 31.1. p,p'-DDD could be measured only in six samples. beta-HCH was the most prevalent HCH isomer with a mean value of 2.08 ng/g ww. The mean concentration of gamma-HCH was 0.38 ng/g ww, while alpha-HCH was not detected in any sample. HCB is found in 95% of the milk samples with a mean concentration of 0.30 ng/g ww. The mean value for the sum of chlordanes was 0.39 ng/g ww, with oxychlordane and trans-nonachlor being the principal contributors. PCBs could be measured only in 8 out of 37 samples and their concentration ranged between <0.15 and 1.92 ng/g ww for the sum of PCBs. PCB profiles were dominated by congeners 153, 180 and 138. PBDEs were detected only in 3 out of 37 samples, with the highest value being 0.014 ng/g ww (0.40 ng/g lipid weight) and BDE 47 was the dominant congener. Although the number of samples is relatively low and they are not representative for the whole Turkish population, the results of the present study are important to provide additional data on the concentrations of persistent organochlorinated pollutants in Turkey and show as first the PBDE levels in Turkish population.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in Finnish semi-domesticated reindeer (Rangifer tarandus tarandus L.)

To explore the concentrations and dynamics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Finnish semi-domesticated reindeer (Rangifer tarandus tarandus L.) the reindeer milk and tissue samples were collected from the sub-arctic northern Finland. Reindeer milk's PCB sum (1.20 ng g(-1) wet weight) and PCDD/F sum (0.70 pg g(-1) ww) in autumn were higher than in summer (PCBs 0.50 ng g(-1) ww and PCDD/Fs 0.20 pg g(-1) ww). The mean fat content in autumn milk (26%) was significantly higher than in summer (10%). Concentrations in reindeer milk were generally far below 50% of that in adult reindeer body burden. However, the bioaccumulation factors were multiple in milk/reindeer calf ratio and that aroused the question of other important exposure routes than lactation. The muscle and liver of reindeer calves had higher PCDD/F and PCB concentrations than adult animals that possibly indicate the significance of transfer of these compounds from dam to calf through lactation and placenta. However, PBDE concentrations were higher in adult reindeer, especially in liver. In addition, reindeer liver seems to have a special feature to collect highly toxic PCDD/Fs, although the PCB sum concentrations (range from 0.33 to 1.69 ng g(-1) wet weight) were clearly higher than the sums of PCDD/Fs (range from 3.78 to 39.2 pg g(-1) ww). Stillborn reindeer calves represented individuals who had got their PCDD/F, PCB and PBDE load only via the placenta. Concentrations in muscle and brown adipose tissue samples did not indicate dependency on fat content. Obviously effective placental transfer of PCBs and PBDEs from reindeer dam to foetus was seen in this study.     

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.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

High concentrations of polybrominated diphenylethers (PBDEs) in breast adipose tissue of California women

We measured major PBDEs and PCBs in breast adipose tissues of California women participating in a breast cancer study in the late 1990s. Samples were analyzed using gas chromatography with electron impact ionization and tandem mass spectrometry detection. The congener profile observed was: BDE47>BDE99>BDE153>BDE100>BDE154 and PCB153>PCB180>PCB138>PCB118. Whereas high correlations were observed within each chemical class, very weak correlations appeared between classes, pointing to different exposure pathways. Weak negative associations were observed for PBDE congeners and age. Our PBDE data are among the highest reported, exceeding data from the National Health and Nutrition Examination Survey and consistent with the high use of PBDEs in California. These data may be helpful in establishing a baseline for PBDE body burdens to gauge changes over time as a result of restrictions in the use of PBDE formulations.     

Market basket study on dietary intake of PCDD/Fs, PCBs, and PBDEs in Finland

We have measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDD/F), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDE) in 10 market baskets consisting of almost 4000 individual food samples representing 228 different food items, and also in the total diet basket. Lower bound concentrations of PCDD/Fs ranged between 0.0057 and 5.6 pg/g fresh weight in the market baskets and the corresponding values for PCBs from 39 to 25,000 pg/g. The fish basket contributed most to the concentrations of dioxins and PCBs, and also to concentrations of PBDEs in which the lower bound range was from 0.82 to 850 pg/g. We also assessed the average daily intakes of these substances by the Finnish adult population. The average daily intake of sum of PCDD/Fs and PCBs as WHO toxic equivalents was assessed to be 115 pg, which was 1.5 pg WHO-TEq/kg body weight using an average mean weight of 76 kg for the general population in Finland. The contribution of fish to the intake of PCDD/Fs was between 94% and 72%, depending on whether lower or upper bound concentrations were used. With respect to PCBs, the contribution of fish was 80%. The calculated intake of PBDEs of 44 ng/day was comparable to intake assessments from other countries. Fish also contributed most to the PBDE intake, but there was some other source of PBDEs that distinguishes the exposure to PBDEs from exposure to PCDD/Fs and PCBs. This additional source seemed to be found in the market basket that included beverages, spices, and sweets.     

Organochlorine pesticide and polychlorinated biphenyl residues in feathers of birds from different trophic levels of South-West Iran

Persistent organochlorine pesticides (OCPs), such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), alpha, beta and gamma-hexachlorocyclohexane (HCH) isomers, together with polychlorinated biphenyl (PCB) congeners (IUPAC Nos. 28, 52, 101, 138, 153 and 180), were determined in tail feathers from 37 birds belonging to 18 species, all originating from the South-West of Iran (Khuzestan, coast of the Persian Gulf). This is the first report on organochlorine contaminants in feathers from museum collections and it is an indication of the concentrations of OCPs and PCBs in the past (1991-1996). Median concentrations of HCHs, DDTs, PCBs and HCB were 22, 14, 11 and 10 ng/g feather, respectively. Significant correlations (p<0.05) were calculated between OCPs (except HCB) and PCBs in the bird feathers. p,p'-DDE and gamma-HCH were the most abundant OCPs, while CB 180, CB 138 and CB 101 were the predominant PCB congeners in almost all species. Significant differences (p<0.05) in the mean concentrations of DDTs and PCBs were detected among species grouped according to their feeding habits. Levels of DDTs and PCBs were highest in the carnivorous species and lowest in the herbivorous species. Levels of OCPs and PCBs in feathers of bids in the 1990s were generally below the thresholds reported to affect reproduction.     

An input-output balance study for PCBs in humans

Polychlorinated biphenyl (PCB) input-output balance studies were performed on five male volunteers, aged between 24 and 30, for periods of 8-14 days in 1998. Dietary exposure was quantified by the duplicate meals method and varied between 220 and 460 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the study period. Dietary intake was dominated by congeners 118, 138, 153 and 180. Average faecal outputs for the five volunteers were 50-290 ng of sigmaPCB (sum of 20 congeners) per day for each of the five individuals over the same period and was dominated by the same four congeners. Whilst the total PCB fluxes were therefore into the body (i.e., accumulation), important differences were noted for different individual congeners. PCBs 44, 47, 49, 52, 60, 66, 101, 105, 110, 118, 149, 151 and 183 all showed net absorption for all five volunteers. Some congeners showed a net absorption in some of the individuals but net excretion in others, as seen by other workers. These congeners (PCBs 138, 153, 180, 187 and 194) are all higher chlorinated congeners and lack meta-para-vicinal hydrogen atoms. There were differences in the net absorption/excretion between individuals, which appeared to be a function of body fat index (BFI). The volunteers with the lowest BFIs showed net excretion for the greatest number of congeners, whilst the individual with the highest BFI was a net absorber of all the congeners studied. The problems in determining and interpreting absorption efficiency values for use in quantitative exposure assessments are discussed. Various factors that influence net absorption of PCBs and other persistent organic pollutants are identified. These include compound properties (including susceptibility to metabolism), the individual's fat status and balance, exposure history and diet.     

Flame retardants and legacy contaminants in polar bears from Alaska, Canada, East Greenland and Svalbard, 2005-2008

Flame retardants and legacy contaminants were analyzed in adipose tissue from 11 circumpolar polar bear (Ursus maritimus) subpopulations in 2005-2008 spanning Alaska east to Svalbard. Although 37 polybrominated diphenyl ethers (PBDEs), total-(α)-hexabromocyclododecane (HBCD), 2 polybrominated biphenyls (PBBs), pentabromotoluene, pentabromoethylbenzene, hexabromobenzene, 1,2-bis(2,4,6-tribromophenoxy(ethane) and decabromodiphenyl ethane were screened, only 4 PBDEs, total-(α-)HBCD and BB153 were consistently found. Geometric mean ΣPBDE (4.6-78.4 ng/g lipid weight (lw)) and BB153 (2.5-81.1 ng/g lw) levels were highest in East Greenland (43.2 and 39.2 ng/g lipid weight (lw), respectively), Svalbard (44.4 and 20.9 ng/g lw) and western (38.6 and 30.1 ng/g lw) and southern Hudson Bay (78.4 and 81.1 ng/g lw). Total-(α)-HBCD levels (<0.3-41.1 ng/g lw) were lower than ΣPBDE levels in all subpopulations except in Svalbard, consistent with greater European HBCD use versus North American pentaBDE product use. ΣPCB levels were high relative to flame retardants as well as other legacy contaminants and increased from west to east (1797-10,537 ng/g lw). ΣCHL levels were highest among legacy organochlorine pesticides and relatively spatially uniform (765-3477 ng/g lw). ΣDDT levels were relatively low and spatially variable (31.5-206 ng/g lw). However, elevated proportions of p,p'-DDT to ΣDDT in Alaska and Beaufort Sea relative to other subpopulations suggested fresh inputs from vector control use in Asia and/or Africa. Comparing earlier circumpolar polar bear studies, ΣPBDE, total-(α)-HBCD, p,p'-DDE and ΣCHL levels consistently declined, whereas levels of other legacy contaminants did not. International regulations have clearly been effective in reducing levels of several legacy contaminants in polar bears relative to historical levels. However, slow or stalling declines of certain historic pollutants like PCBs and a complex mixture of "new" chemicals continue to be of concern to polar bear health and that of their arctic marine ecosystems.     

Biomagnification of anthropogenic and naturally-produced organobrominated compounds in a marine food web from Sydney Harbour, Australia

Polybrominated diphenyl ethers (PBDEs) and naturally-produced organobrominated compounds, such as methoxylated PBDEs (MeO-PBDEs), have been scarcely studied in the Southern Hemisphere. Yet, sources of the latter group of compounds were found in Southern regions, specifically in Australia. The environmental distribution and biomagnification potential of organobrominated compounds were therefore investigated in a representative aquatic food chain (invertebrates and fish) from the Sydney Harbour, Australia. Mean PBDE concentrations ranged from 6.4 ng/g lipid weight (lw) in squid to 115 ng/g lw in flounder. BDE 47 was the dominant congener, followed by BDE 100. Mean levels of MeO-PBDEs (sum of congeners 2’-MeO-BDE 68 and 6-MeO-BDE 47) were as high as 110 ng/g lw in tailor, with a slight dominance of 2’-MeO-BDE 68. Polybrominated hexahydroxanthene derivates (PBHDs), another class of naturally-produced compounds, were found at variable concentrations and ranged from 4.7 ng/g lw in fanbelly and 146 ng/g lw in tailor. The tribrominated PBHD isomer dominated in the samples, except for luderick and squid. The lower levels of PBDEs found in luderick from the harbour compared to those obtained from the upper Parramatta River indicated a terrestrial (anthropogenic) origin of PBDEs, while the higher levels of MeO-PBDEs and PBHDs in the samples from the harbour confirmed the marine (natural) origin of these compounds. The highest trophic magnification factor (TMF) was found for sum PBDEs (3.9), while TMFs for sum MeO-PBDEs and sum PBHDs were 2.9 and 3.4, respectively. This suggests that biomagnification occurs in the studied aquatic food chain for anthropogenic brominated compounds, but also for the naturally-produced organobromines.     

Concentrations of PCDD/Fs,PCBs and PBDEs in breast milk of women from Catalonia,Spain: A follow-up study

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in two previous surveys carried out in 1998 (baseline study) and 2002. The current concentrations of PCDD/Fs in breast milk ranged from 45 to 143 pg/g fat (2.8 to 11.2 pg WHO-TEQ/g fat), while total PCBs ranged from 114 to 617 pg/g fat (2.8 to 17.6 pg WHO-TEQ/g fat). PBDE concentrations (sum 15 congeners) ranged from 0.57 ng/g fat to 5.9 ng/g fat, with a mean value of 2.5 ng/g fat. A general decrease of the concentrations for PCDD/Fs and both planar and total PCBs was observed. Regarding to PBDE concentrations in breast milk, similar levels between the 2002 and the present study were noted. The levels of PCDD/Fs and PCBs in milk of women living in urban areas were higher than those corresponding to the industrial zones (38% and 40%, respectively). However, the current PBDE levels were slightly lower (13%) in the urban than in the industrial zone. For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants found in recent studies carried out in the same area of study.     

Concentrations of chlorinated and brominated contaminants and their metabolites in serum of harbour seals and harbour porpoises

Harbour seals (Phoca vitulina) and harbour porpoises (Phocoena phocoena) are top predators in the North Sea and consequently accumulate a variety of pollutants in their tissues. Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and their hydroxylated metabolites (HO-PCBs and HO-PBDEs) were measured in serum of wild harbour seals (n = 47) and captive harbour porpoises (n = 21). Both species exhibit long life spans and do not have extreme situations, such as complete fasting during periods of lactation, in their annual cycles. For PCBs, concentrations in adult males were slightly higher than in juveniles and lowest in juvenile females. For PBDEs, juveniles have higher levels than adult males and females, probably as a consequence of lactational transfer. However, differences between these age–gender groups were not statistical significant, indicating that individual variation was limited within each species, even without knowing the feeding status of the animals. Body condition, particularly emaciation, has a major influence on the levels of chlorinated and brominated contaminants in serum. Profiles of PCBs were CB 153 > CB 138 > CB 187 > CB 180 and CB 153 > CB 138 > CB 149 > CB 187 > CB 180 for harbour seals and porpoises respectively. For PBDEs, BDE 47 was the predominant congener followed by BDE 100 and 99 in both species. In harbour seals, concentrations of sum PCBs (median: 39,200 pg/ml) were more than 200 times higher than levels of sum PBDEs (median: 130 pg/ml) and almost 10 times higher than concentrations of sum HO-PCBs (4350 pg/ml). In harbour porpoises, concentrations of sum PCBs (median: 24,300 pg/ml) were about 20 times higher than concentrations of PBDEs (median: 1300 pg/ml). HO-PCBs were detected in only 4 harbour porpoises and this at very low concentrations. Naturally-produced MeO-PBDEs were only found in harbour porpoises at concentrations ranging from 120 to 810 pg/ml. HO-PBDEs were not found in any species. In general, harbour seals accumulate less compounds and have mostly lower concentrations than harbour porpoises possibly as a result of a better developed metabolism.     

Variation, levels and profiles of organochlorines and brominated flame retardants in great tit (Parus major) eggs from different types of sampling locations in Flanders (Belgium)

Small-scale geographical variation in the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated using the eggs of a terrestrial residential songbird species, the great tit (Parus major). In addition, we investigated the influence of the type of sampling location on the presence of these pollutants. To achieve this, 10 different sampling locations in Flanders (Belgium) were classified into 3 groups based on the extent of urbanisation, industrialisation and agriculture. The higher variance among sampling locations for the levels and profiles of PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. Levels of PCBs and PBDEs were significantly higher in the industrialised sampling locations compared to the other locations. Sum PCB and sum PBDE levels reached up to 6050 and 79 ng/g lipid weight, respectively. PCBs and PBDEs were highly positively correlated for all groups, suggesting similar exposure pathways and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs up to 2683 ng/g lipid weight) were detected in the rural sampling locations situated in a residential area. This suggests that local historical usage of OCPs by inhabitants may be an important source of contamination in Flanders. Contamination profiles differed also among the sampling locations. The rural sampling locations had a higher contribution of lower brominated BDE congeners, whereas the industrialised locations had a higher contribution of higher brominated congeners. The differences in contamination profiles among the sampling locations are probably due to differences in exposure. In conclusion, our results showed that the characteristics of a sampling location influence both the levels and profiles of PCBs, OCPs and PBDEs.     

Organohalogenated pollutants in human serum from Iassy, Romania and their relation with age and gender

Human serum samples (n=142) from Iassy county (Eastern Romania) collected in 2005 were analyzed for p,p'-DDT and its metabolites, hexachlorobenzene, hexachlorocyclohexane (HCH) isomers, chlordane and metabolites and 14 polychlorinated biphenyl (PCB) congeners. In all samples, p,p'-DDE (principal metabolite of p,p'-DDT) and beta-HCH (most persistent HCH isomer) were the most abundant organochlorine pesticides (OCPs) with median concentrations of 1975 and 923 ng/g lipid weight (lw), respectively. Hexachlorobenzene and p,p'-DDT were also detected in all samples, but at a lower median concentration of 30 and 340 ng/g lw, respectively. The large variation of the ratio p,p'-DDT/p,p'-DDE (range between 0.02 and 0.80) suggests various degrees of exposure to DDT, including recent exposure, at least to some subgroups of the population. Chlordane and its metabolites were in most cases close to the limit of quantification suggesting a very low use of chlordane formulations in Eastern Romania. Unexpectedly, PCBs were present in all samples at sometimes considerable levels (up to 4970 ng/g lw for sum of 14 PCB congeners) indicating a higher exposure of the Romanian population than previously reported. The PCB profile consisted of persistent congeners such as 138, 153, 170 and 180 which contributed for approximately 75% to the sum PCBs. Concentrations of most pollutants correlated significantly with age (r>0.86, p<0.01). Except for p,p'-DDT and gamma-HCH, the mean levels of OCPs in females were statistically higher than in males, while, except for octa-CBs, no gender differences were found for PCBs. Levels of p,p'-DDE, penta-CBs, hexa-CBs and hepta-CBs were significantly higher in individuals with a rural main residence. In a pooled serum sample, 6 polybrominated diphenyl ether (PBDE) congeners were measured at a level of 1.04 ng/g lw. Compared to results available from Central and Eastern European countries, human serum samples from Romania contained higher levels of contamination. This emphasizes that an extensive and rigorous program for the monitoring of OCPs and PCBs in Romanian population is highly needed in the light of possible adverse health effects acknowledged for these pollutants.