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.     

Reconstruction of historical trends of PCDD/Fs and PCBs in the Venice Lagoon, Italy

Historical trends of PCDD/Fs and PCBs from the year 1900 have been reconstructed for the Venice Lagoon area by using a fugacity-based dynamic multimedia model. A novel approach to estimate the inputs to the system was applied. Emissions to the lagoon were estimated by studying dated sediment cores taken from salt marshes located in the lagoon area. These cores have recently proven to be a suitable tool to reconstruct the temporal trends of atmospheric deposition of POPs. According to the model, concentrations of PCBs and PCDD/Fs in air and water reflect the trends of their production and usage, peaking during the 1960s. The peaks in the sediment were delayed by 5-40 years depending on the congener. Predicted concentrations are in good agreement with experimental results. The most important input parameters, identified by a sensitivity analysis, are the degradation constants, K(ow), the Henry's law constant, vapour pressure, active sediment depth, sediment resuspension, and deposition rates, and water residence time in the lagoon.     

Concentrations of PCDD/PCDFs and PCBs in retail foods and an assessment of dietary intake for local population of Shenzhen in China

OBJECTIVES: Concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 18 polychlorinated biphenyls (PCBs) were measured in 11 varieties of food groups collected from retail market of Shenzhen, Guangdong province, China from 2004 to 2006. PCDD/Fs and PCBs dietary intake from varies food for the local population was estimated in the study. METHODS: Concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (PCBs) as well as 6 marker PCBs were measured in 11 varieties of food groups in total 110 food samples by isotope dilution HRGC/HRMS. PCDD/Fs and PCBs dietary intake for local population was estimated using total WHO-TEQ concentration and different food consumption amount of the local population. RESULTS: The median WHO-TEQ concentrations of sum of PCDD/Fs and DL-PCBs varied from 0.0093 pg/g (parts per trillion) in vegetable to 9.89 pg/g in fish. Fish was followed by egg 2.46, chicken 1.73, beef 0.94, mutton 0.82, duck 0.39, pork 0.37, milk powder 0.25, vegetable oil 0.076, cereals 0.022 pg/g and vegetable. The monthly intake of PCDD/Fs and PCBs were 40.9 pg WHO-TEQ/kg b.w. for local population. Sum of fish, livestock, and poultry contributed 77% to the Estimated Monthly Intake (EMI) in local population. CONCLUSION: Estimated dietary intake of PCDD/Fs and DL-PCBs for local population was below the provisional tolerable monthly intake(PTMI) set by Joint FAO/WHO Expert Committee on Food Additives (JECFA).     

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.     

Concentrations of PCDD/PCDFs and PCBs in fish and seafood from the Catalan (Spain) market: estimated human intake

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) in samples from 14 fish and seafood species widely consumed by the population of Catalonia, Spain, were measured. These samples were randomly purchased independently of their geographical origin. The intake of PCDD/Fs and PCBs through consumption of these species was also estimated for various age and sex groups of this population. The highest and lowest levels of PCDD/Fs and dioxin-like PCBs (DL-PCBs) were found in red mullet and shrimp, respectively. For a standard adult man (70 kg body weight), the intake of PCDD/Fs plus DL-PCBs through consumption of fish and other seafood was estimated to be 38.0 pg WHO-TEQ/day. Tuna, hake, and sardine were the species with the highest contribution to this intake. The results of this study indicate that, in general terms, the dietary habits of the population of Catalonia (Spain) regarding fish and seafood consumption do not contribute remarkably to increase PCDD/F and DL-PCB intake.     

Natural and synthetic endocrine disrupting compounds (EDCs) in water, sediment and biota of a coastal lagoon

We report a survey on the occurrence and distribution of natural (17beta-estradiol, E2; estrone, E1) and synthetic (nonylphenol, NP; nonylphenol monoethoxylate carboxylate, NP1EC; bisphenol-A, BPA; benzophenone, BP; mestranol, MES; 17alpha-ethinylestradiol, EE2; diethylstilbestrol, DES) endocrine disrupting compounds (EDCs) in water, sediment and biota (Mediterranean mussel, Mytilus galloprovincialis) in the Venice lagoon, a highly urbanized coastal water ecosystem that receives both industrial and municipal wastewater effluents. The survey was preceded by the development of tailor made extraction and clean-up procedures for the simultaneous HPLC-ESI-MS determination of all examined EDCs in sediment and biota samples. Satisfactory extraction performances and method detection limits (MDLs) were obtained for almost all EDCs. Most of the selected compounds were found in water and sediment (concentration range: 2.8-211 ng/L, and 3.1-289 microg/kg, d.w., respectively), while only 17alpha-ethinylestradiol and nonylphenol were recorded in biota samples (conc. range: 7.2-240 ng/g, d.w.). 17beta-estradiol and ethinylestradiol contributed mostly to the water estradiol equivalent concentration (EEQ) (1.1-191 ng/L, average: 25 ng/L), while synthetic EDCs (17alpha-ethinylestradiol, diethylstilbestrol) were mainly responsible of the sediment EEQ (1.1-191 microg/kg, average: 71 microg/kg, d.w.). Whenever diethylstilbestrol was not recorded in the sediment, water EEQs were similar to sediment EEQs. A remarkable increase of nonylphenol was observed in sediments over the last decade.     

The bioaccessibility of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) in cooked plant and animal origin foods

In this study, we compared the effect of boiling and frying food preparation methods in determining the bioaccessibility of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) in rice, cabbage, milk powder, eggs, beef, and fresh water fish. We then used these data to calculate a toxic equivalent (TEQ) for risk assessment and compared it to published values that did not account for bioaccessibility.When the foods were prepared by boiling, the mean bioaccessibility (%) in rice (PCBs: 16.5 ± 1.0, PCDD/Fs: 4.9 ± 0.3) and cabbage (PCBs: 4.2 ± 0.9, PCDD/Fs: 1.9 ± 0.7) were lower than in animal origin foods (beef, PCBs: 49.0 ± 3.3, PCDD/Fs: 7.8 ± 0.9; egg, PCBs: 29.7 ± 3.1, PCDD/Fs: 8.6 ± 1.3; fish, PCBs: 26.9 ± 2.5, PCDD/Fs: 7.9 ± 1.3; milk powder, PCBs: 72.3 ± 1.6, PCDD/Fs: 28.4 ± 1.2).When fried in cooking oil, the bioaccessibilities of all analytes in all foods increased, but the increase in plant based foods (rice, PCBs: 3.4 ×, PCDD/Fs: 3.6 ×; cabbage, PCBs: 10.3 ×, PCDD/Fs: 7.9 ×) was greater than that of animal origin foods (beef, PCBs: 1.6 ×, PCDD/Fs: 3.4 ×; egg, PCBs: 2.1 ×, PCDD/Fs: 1.8 ×; fish, PCBs: 2.8, PCDD/Fs: 3.2 ×).Comparison of PCBs/PCDD/Fs bioaccessibility in rice and cabbage showed that bioaccessibility was greater in the low fat, high carbohydrate/protein content food (rice) than in the low carbohydrate/protein, low fat content food (cabbage), regardless of the method used to prepare the food.Adjusting for bioaccessibility reduced the gross estimated daily intake (EDI) of 112 pg WHO-TEQ/day, by 88% and 63% respectively for foods prepared by boiling and frying.Our results indicate that: 1) The method used for cooking is an important determinant of PCBs/PCDD/Fs bioaccessibility, especially for plant origin foods, 2) there might be a joint fat, carbohydrate and protein effect that influences the bioaccessibilities of PCBs/PCDD/Fs in foods, and 3) use of bioaccessibility estimates would reduce the uncertainty in TEQ calculations.     

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.     

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.     

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

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

E-waste recycling induced polybrominated diphenyl ethers, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzo-furans pollution in the ambient environment

Polybrominated diphenyl ethers (PBDEs) have been determined in 30 samples, including soil, biota and plant collected from an electronic waste recycling site and its vicinage towns. Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) were also simultaneously analyzed in 20 samples. PBDEs were detected in all soil samples and the highest was up to 789 ng/g dry weight (dw). The toxic equivalency (TEQ) of PCBs and PCDD/Fs detected in E-waste recycling site is significant higher than those in the vicinage samples. Biota and plant were also contaminated with high level of PBDEs, PCBs and PCDD/Fs in this area. High levels of the three kinds of organic compounds in the environmental samples showed that the E-waste recycling have induced serious environmental problems.     

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.     

Levels of PCDD/PCDFs and PCBs in edible marine species and human intake: a literature review

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) are lipophilic organic compounds whose origin comes from many different sources. PCDD/Fs and PCBs are ubiquitous and persistent environmental pollutants with a well known potential toxicity, which were included at the 1998 UN-EC POP protocol. Although human exposure to PCDD/Fs and PCBs can occur by various routes, food is the primary source. A number of studies have shown that the major food sources of these organic pollutants are fat-containing animal products, including fish and other seafood. Because of the frequent health recommendations concerning fish consumption, to determine the contribution to the dietary intake of chemical contaminants such as PCDD/Fs and PCBs through fish and other seafood consumption is an issue of special interest. This paper reviews the state of the science regarding recent literature on PCDD/F and PCB levels in marine species and human intake through fish and seafood consumption. The concentrations of these pollutants depend basically on the environment in which the respective species are caught. It is concluded that some groups of population frequently consuming high quantities of certain species could be significantly increasing health risks due to PCDD/F and PCB exposure.     

Bioaccumulation of PCDD/Fs,PCBs and PBDEs by earthworms in field soils of an E-waste dismantling area in China

A total of 60 paired samples of earthworm, corresponding soil and wormcast were collected to investigate the bioaccumulation tendency of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in earthworms from a typical E-waste dismantling area in east China. Significant correlations were observed for the total concentrations among different matrix types except for PCDD/Fs in soil and earthworm. The bioaccumulation tendency showed some differences among the contaminants. Calculated biota–soil accumulation factors (BSAFs) indicated that PCBs and PBDEs had higher bioaccumulation potential compared to PCDD/Fs, which was somewhat different from laboratory studies. The plot of mean BSAFs versus log K_ow values for PCBs and PBDEs was well fitted by a second-order polynomial with the maximum BSAF at approximately log K_ow of 6.5. While for PCDD/Fs, only a slightly decreasing trend was observed with increasing log K_ow. Composition analysis indicated that tetra-, penta- and hexa-halogenated homologs had higher bioaccumulation levels, indicating that medium-halogenated congeners with log K_ow around 6.5 are more easily accumulated by earthworms. Furthermore, the ratios of BDE-47/-99 and BDE-99/-100 showed some discrepancies with the technical products and other biotic species, suggesting different bioaccumulation potential of PBDEs in earthworm.     

Atmospheric bulk deposition to the lagoon of Venice Part I. Fluxes of metals, nutrients and organic contaminants

First available data on atmospheric fall-out were provided by sampling monthly bulk depositions in four sites inside the Lagoon of Venice (550 km2). Sampling was carried out monthly during the period July 1998-July 1999, in one site near an industrial area (Porto Marghera; site D), another site in the city of Venice (site A), and the remaining two in the southern- and northernmost ends of the Lagoon (Valle Figheri, site C; Valle Dogà site B). The following determinations were carried out for each samples: pH, conductivity, grain-size, particulate load, and dissolved nutrients (N, P). Samples were then subdivided into soluble and insoluble fractions, and Al, Ca, Na, K, Mg, Si, Mn, Fe, Zn, Ni, Cr, Cu, Pb, Cd, As, Hg, Ti, V, S, P, Se and Sb were analysed on both fractions. Total organic micropollutants (PAH, PCB, HCB, DDT, PCDD/F) were measured. As regards particle size distribution, there was great variability among sampling sites. The percentage of the < or =2 microm grain-size fraction was higher in the southern and northern ends of the Lagoon. Small differences were found among sites for major elements, whereas higher variability was observed for inorganic and organic micropollutants, with standard deviations between 20% and 60% of the fluxes measured. Major differences in annual fluxes between the most polluted sites (mostly D and A) and background (site B) were seen for Cd (0.26 vs. 0.06 mg m(-2) year(-1)), Hg (41 vs. 15 microg m(-2) year(-1)), PCB ( approximately 2500 vs. approximately 500 ng m(-2) year(-1)) and HCB ( approximately 8000 vs. approximately 1000 ng m(-2) year(-1)). Comparisons with previous data, collected in the periods 1993-1994 and 1995-1997, were only available for a few trace metals. A definite decline in the annual Pb flux in the city of Venice was detected, from 18 to 13 mg m(-2) in 1996/1997 and 1995/1996 respectively, to approximately 5 mg m(-2) in the present study. Total annual deposition was calculated by means of two different methods, which gave very similar results: (i) the mean value of deposition in the four sites was multiplied by lagoon area (550 km2); (ii) the monthly rain isopleths were combined to normalize deposition values. The figures are: 15-34 kg of Hg and Sb, approximately 200 kg of As, approximately 100 kg of Cd and PAH, 0.7-1.3 tons of Cr, Ni and V, more than 2 tons of Cu and Pb, 17 of Zn, 55 of total P, approximately 200 of Al, and 3900 of DIN. Total fluxes of organics inside the lagoon were: PAH approximately 100 kg; HCB approximately 1 kg; DDT approximately 0.4 kg. PCB and PCDD/F fluxes were approximately 500 g and approximately 10 g, corresponding respectively to 0.1 and 0.4 g I-TE. The correlations between fluxes of inorganic micropollutants and grain-size were significant. Multivariate statistical analysis was applied to investigate more accurately relationships between the insoluble and dissolved fractions of inorganic micropollutants and grain-size fractions. In particular, significant correlations were highlighted between the dissolved fraction of As and the < or =1 mum particle size fraction. Relations between levels of SigmaPCDDF, SigmaPCDD, PCB and PAH congeners and grain-size revealed significant correlation coefficients for the remote sites (B, C), and none in the urban and industrial sites (A, D). In particular, significant correlations were highlighted between SigmaPCDDF, SigmaPCDD and particle size fraction < or =2 mum, and between benzo(a)pyrene and PCB 167 and particle size fraction 4-8 mum.     

Analysis of human milk to assess exposure to PAHs,PCBs and organochlorine pesticides in the vicinity Mediterranean city Mersin,Turkey

Assessment of human exposure to environmental persistent organic pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) based on the levels in human breast milk provides a reasonable tool not only to assess the contaminant burden in mothers but also to assess potential exposure of breast-fed neonates. There are limited data on levels of PCBs and OCPs in humans but no previous reports from Turkey on chemically determined levels PAHs in human milk. The aim of this study was to report the levels and accumulation profiles of OCPs, PCBs and PAHs in 47 breast milk samples obtained from a Mediterranean city, Mersin. High resolution analyses were performed by a gas chromatography coupled with mass spectrometer (GC–MS). Dichlorodiphenyldichloroethane (4.4′-DDE) was the dominant pollutant. Beta-hexachlorocyclohexane (ß-HCH), dichlorodiphenyltrichloroethane (4.4′-DDT), dieldrin, hexachlorobenzene, oxy-chlordane, cis-heptachlorepoxide were the other main OCPs detected. Mean levels of ΣPCB congeners and WHO_PCB-TEQ were 9.94 and 0.001 ng/g lipid, respectively. PCB 153 showed the highest concentration (3.37 ng/g lipid), followed by PCB 138 and 180. For the dioxin-like PCBs, PCB 118 was the dominant (0.97 ng/g lipid). Naphthalene, phenanthrene, pyrene and fluoranthene were the major PAHs among the 16 PAHs detected. The estimated daily intakes of DDTs, PCBs, HCHs and HCB were not exceeded the tolerable daily intake (TDI) proposed by the Health Canada Guideline. These results indicate that the neonates of Mersin city are exposed to persistent organic pollutants analyzed in this study. However, neonates born in Mersin province are less exposed than the ones born in other regions, considering OCP and PCB levels in breast milk.     

PCDD/F levels in the neighbourhood of a municipal solid waste incinerator after introduction of technical improvements in the facility

In 1998 and 1999, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in soil and herbage samples collected in the vicinity of an old municipal solid waste incinerator (MSWI) (S. Adrià del Besòs, Barcelona, Spain). Just after the 1999 collection, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in this facility. The purpose of the present study was to determine the current concentrations of PCDD/Fs in soil and herbage samples collected in the neighbourhood of the MSWI and to compare these concentrations with those obtained in the 1998 and 1999 surveys. During the period 1998-1999, an increase of 31% (P>.05) was found in the median PCDD/F levels in soils, while a reduction of 40% (P>.05) was observed in the period 1999-2000. Similarly, in the period 1998-1999 an increase of 41% (P>.05) was found in the levels of PCDD/Fs in vegetation, while a 30% decrease (P<.05) was seen in the period 1999-2000. Although after introduction of the technical improvements in the MSWI a notable reduction in the levels of PCDD/Fs in soil and vegetation has been noted, the median decreases have not been as great as it could be expected according to the very pronounced reductions in PCDD/F emissions from the stack. It indicates that other emission sources of PCDD/Fs also have a notable impact on the area under direct influence of the MSWI.     

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.     

Health risk assessment of PCDD/F emissions from a hazardous and medical waste incinerator in Turkey

A multimedia risk assessment procedure was conducted to determine the fate and transport of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/F) emissions from the Izmit Hazardous and Medical Waste Incinerator (IZAYDAS) in Turkey and their potential health risks. Congener concentrations in ambient air and their deposition rates were determined by an air dispersion model (ISCST3). Their transfer to some plant groups and animal tissues was predicted by food chain modeling. Exposure scenarios were produced based on three receptor groups (urban, semiurban, and rural) and five subgroups determined according to ages. Daily intakes of PCDD/Fs via exposure pathways were determined based on three different emission scenarios for each group and subgroup. Estimated incremental PCDD/F doses caused by the incinerator emissions in central-tendency scenario were computed as between 2.31 x 10(-6) and 0.008 pg TEQ kg(-1) bodyweight (bw) day(-1) on average for all the receptors other than infants in all the settings, while the range was 3.01 x 10(-5)-0.081 pg TEQ kg(-1) bw day(-1) for infants. Sensitivity analysis showed that the consumption of vegetal products and their locally grown fractions are the most significant parameters in the exposure to PCDD/Fs in the area.     

Levels and distribution of organochlorines in fish from Indonesia

Organochlorines such as PCBs, DDTs, HCHs, CHLs and HCB were determined in pooled whole body homogenized of fish samples collected from five locations during 1998 and 2003 in order to understand their contamination status, temporal and spatial variation in Indonesian waters. PCBs and DDTs were the predominant contaminants with concentrations from 9.7 to 2700 ng/g lipid wt. and 12 to 1100 ng/g lipid wt., respectively, while HCHs (nd-24 ng/g lipid wt.), CHL compounds (nd-81 ng/g lipid wt.) and HCB (0.22-28 ng/g lipid wt.) were one to two orders of magnitude lower. Among the locations, PCBs and CHLs were higher in the samples from highly industrialized and thickly populated-locations, whereas OC pesticides such as DDTs and HCHs were particularly more prominent in suburban and rural areas. Levels of OCs observed in the waters surrounding Java Island were higher than those in Sumatra Island, implying significant use of OCs in highly populated Java Island. Concentrations of PCBs and DDTs in fish from Jakarta Bay were significantly lower in the samples collected in 2003 as compared to fish in 1998, indicating decreasing trend of these compounds in the Indonesian environment. Recent estimated average daily intakes of PCBs (0.81 microg/person/day), DDTs (1.1 microg/person/day), HCHs (0.018 microg/person/day), CHLs (0.010 microg/person/day) were much lower than the threshold values recommended by various agencies, suggesting minimal risk of this compound via fish ingestion to Indonesians.