Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland

A total of 156 fish composite samples were collected from five areas of the Baltic Sea and from three lakes and analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The European Union's maximum permissible level for PCDD/Fs, 4 pg WHO-TEQ/g fresh weight (fw), was exceeded in salmon, river lamprey and Baltic herring. In other species from the Baltic Sea, the 90th percentile was 3.42 pg WHO(PCDD/F)-TEQ/g fw. In the lake fish, the concentrations of PCDD/Fs, PCBs and PCNs were only 29-46% of those in the same species caught from the Baltic Sea, whereas the concentrations of PBDEs in the lake fish were as high as in the Baltic Sea fish. Dioxin-like PCBs contributed to the total dioxin-like toxicity of PCBs and PCDD/Fs by 49+/-12% in all the analysed samples.     

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.     

Contamination of River Kymijoki sediments with polychlorinated dibenzo-p-dioxins, dibenzofurans and mercury and their transport to the Gulf of Finland in the Baltic Sea

Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as the chemical industry. Up to 24,000 ton of wood preservative, chlorophenol known as Ky-5, was manufactured in the upper reaches of the river, an unknown amount of which was discharged into the river between 1940 and 1984. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurred as impurities in the final Ky-5 product. The PCDD/F concentrations and burden in the river sediments were studied and the transport of PCDD/Fs from contaminated sites downstream and into the Gulf of Finland in the Baltic Sea was estimated. More than 190 sediment cores were sampled to estimate the volume of contaminated sediments and the total PCDD/F burden. The transport of PCDD/Fs was estimated using sediment traps placed at several sites. The survey revealed that sediments in the river were heavily polluted by PCDD/Fs, the main toxic congener being 1,2,3,4,6,7,8-heptachlorodibenzofuran, a major contaminant in the Ky-5 product. The mean total concentration at the most polluted river site downstream from the main source was 42000 microg kg(-1) d.w. (106 microg I-TEQ kg(-1)). The elevated concentrations in the coastal region and the present estimated transport from the River Kymijoki confirm earlier assessments that the river is a major source of PCDD/F for the Gulf of Finland.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Investigation of PCDD/Fs and dl-PCBs in fish from the southern Baltic Sea during the 2002–2006 period

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in the southern Baltic herring (Clupea harengus), sprat (Sprattus sprattus), and salmon (Salmo salar) are reported.The significant interspecies and season-specific differences in PCDD/Fs and dl-PCBs concentrations were observed. The contribution of dl-PCBs to the total toxicity equivalents (TEQs) ranged between 50% and 70%, dependently on fish species. In all samples, concentrations of PCDF were higher in comparison with that of PCDD.The permissible limits of the content of PCDD/Fs and dl-PCBs (8 pg g⁻¹ fresh weight for the sum of PCDD/Fs and dl-PCBs, and 4 pg g⁻¹ fresh weight for the PCDD/Fs) were exceeded mainly in salmon samples (in 80% of salmon samples studied). The elevated levels of PCDD/F and dl-PCB were observed only in two of seventy two herring samples, and in ten of 62 sprat samples.The multiple regression analysis revealed that fish lipid content, and concentration of PCB 153, used simultaneously, might be useful in the prediction of TEQ values of fish samples. These two variables explained more than 80% of total variance. For all fish species studied, the correlation coefficients obtained with the multiple regression analysis were higher than that obtained with the regression analysis involving total TEQ values, and only one independent variable: fish lipid content.     

Marine and farmed fish on the Polish market: Comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins – A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Dioxin concentrations in sediments of the Baltic Sea--a survey of existing data

Recent survey results for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins) in Baltic Sea sediments from Finland, Sweden and Denmark were merged with previously published Baltic Sea data. Regional distribution of concentration levels, differences in congener patterns, and temporal changes in sediment profiles were examined. One of the main objectives was to study if any major point sources for different PCDD/F congeners could be identified on a regional scale, based on sediment records. The survey confirmed the impact of chlorophenol production derived highly chlorinated PCDF-congeners on the total toxicity in sediments in the Gulf of Finland near the Kymijoki river estuary. Signatures of other point sources or combined point sources pertinent to specific industry branches or particular production processes (such as pulp bleaching, vinyl chloride production, thermal processes) may be discerned. However, the findings did not support any of the known point sources significantly influencing those congeners that are most abundant in Baltic herring and salmon. Instead, regional distributions in the Baltic Sea indicate that atmospheric deposition may act as a major source for those congeners and especially for 2,3,4,7,8-PeCDF. There were clear indications of declines in levels in sediment in some areas, but generally the levels of highly chlorinated PCDD/Fs on the northern coast of the Gulf of Finland were still high when compared with other areas of the Baltic Sea. Major areas with data gaps cover the south-eastern and eastern coastal regions of the Baltic Proper and the southern Gulf of Finland.     

Levels of PCDD/F and dioxin-like PCB in Baltic fish of different age and gender

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) in Baltic Sea fish like herring (Clupea harengus membras), sprat (Sprattus sprattus balticus), perch (Perca fluviatilis), pikeperch (Sander lucioperca) and flounder (Platichthys flesus trachurus) collected from four areas of the Estonian coastal waters are reported. All samples are studied for their relationship between the length (cm) and wet weight (g); length (cm) and age (years); lipid content and dry matter. The level of PCDD/F and PCB concentrations in younger 1-5 years old Baltic herring and sprat collected in 2002-2005 from the eastern and central parts of the Gulf of Finland, Gulf of Riga and Open Baltic Sea (Central Baltic) is related to the fish age and compared with those found in the 1990s. In addition, PCDD/F and PCB concentrations of different age groups herring, sprat, perch, pikeperch and flounder collected in 2003-2004 from the Lake Peipsi, Gulf of Finland, Gulf of Riga and Open Baltic Sea are related also to their age. Consequently, it was manifested that in older Baltic fish the concentrations of PCDD/F and PCB were higher than in the younger age groups. By the help of principle component analysis (PCA) the effect of gender on the concentrations of PCDD/F for the juvenile Baltic herring and sprat collected in 2004-2005 is investigated for the first time. It was summarized that the biological factor age plays a large role for the contamination of the fish with important toxic organohalogenated compounds such as PCDD/F.     

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 biphenyls in the general population in Finland

We measured adipose tissue concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs) in 420 general Finns living in southern Finland. The mean (median) concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 29.0 (24.1) and 20.7 (16.7) pg g-1 fat, respectively. The concentrations clearly correlated with age. Expressing the concentrations as a function of subject's ages revealed that the exposure of Finns has declined over the last 30 years. A downward gradient was found in the concentrations from the Baltic Sea coast to inland areas in Finland, and this was assessed to be due to consumption of the Baltic Sea fish, especially Baltic herring. Linear regression models for natural logarithm WHO(PCDD/F)-TEQ, natural logarithm WHO(PCB)-TEQ, and natural logarithm WHO(total)-TEQ, explained 70%, 69%, and 72% of the variability, respectively. Age, lactation, place of residence, and fish consumption frequencies were significant predictors in the models.     

Human dietary intake of organochlorines from Baltic herring: implications of individual fish variability and fisheries management

This study examines the extent to which Finnish human dietary intake of organochlorines (PCDD/Fs and PCBs) originating from Northern Baltic herring can be influenced by fisheries management. This was investigated by estimation of human intake using versatile modeling tools (e.g., a herring population model and a bioenergetics model). We used a probabilistic approach to account for the variation in human intake of organochlorines originating from the variation among herring individuals. Our estimates were compared with present precautionary limits and recommendation for use. The results show that present consumption levels and frequencies of herring give a high probability of exceeding recommended intake limits of PCDD/Fs and PCBs. Furthermore, our results clearly demonstrate that in the risk management of dioxinlike organochlorines, regulating fishing (in this case increasing fishing pressure) is a far less effective way to decrease the risk than regulating the consumption of herring. Increased fishing would only slightly decrease organochlorine concentrations of herring in the Finnish fish market.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Sedimentation of PCDD/Fs and PCBs in the Gulf of Finland and the Gulf of Bothnia,the Baltic Sea

Sediment trap material was collected during May–December in the period 1996–2008 in three coastal areas and four open sea stations in the Finnish territory of the Baltic Sea. The highest sedimentation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with a typical source-related congener profile from chlorophenol production dominated by highly chlorinated dibenzofurans was found close to a historical source in the Kymijoki estuary. This was an order of magnitude higher than in other river estuaries and two orders of magnitude higher than in the open sea stations. The sedimentation of polychlorinated biphenyls (PCBs) was also higher in river estuaries than in other areas. No significant decrease over a 12 year period of monitoring was found in concentration or in sedimentation in the Kymijoki estuary. In the western Gulf of Finland, the Archipelago Sea and the Gulf of Bothnia, the dominating congeners, calculated as toxic equivalent (TEQ) in sedimentation were 1, 2, 3, 7, 8-PeCDD and 2, 3, 4, 7, 8-PeCDF, often reported as the main congeners in deposition.     

Structure-related distribution of PCDD/Fs, PCBs and HCB in a river-sea system

Water concentrations of PCDD/Fs, HCB, and non-ortho, mono-ortho, and non-dioxin-like PCBs were measured four times during 1 year in a coastal area of the Baltic Sea, to investigate background levels and distribution behaviour. Sampling sites included two rivers, an estuary, and the sea. Particulate and apparently dissolved concentrations were determined using active sampling (filters + PUFs), while freely dissolved concentrations were determined using passive sampling (POM-samplers). The distribution between particulate + colloidal and freely dissolved phases, in the form of TOC-normalized distribution ratios (K_TOC), was found to be near or at equilibrium. The observed K_TOC were not significantly different between sampling sites or seasons. For PCDD/Fs, the concentrations were significantly correlated to suspended particulate matter (SPM), while no correlation to organic carbon (TOC) was observed. In the estuary and the sea, PCB concentrations were correlated to TOC. The sorption of various congeners to SPM and TOC appeared to be related to both hydrophobicity and 3D-structure. The PCDD/F concentration in the sea decreased to one third in May, likely connected to the increased vertical flux of particles during the spring bloom.     

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.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Organochlorine compounds (PCBs, PCDDs and PCDFs) in seafish and seafood from the Spanish Atlantic Southwest Coast

Concentrations and congener specific profiles of PCDD/Fs and PCBs were determined in edible fish and seafood species from the Coast of Huelva, in the Spanish southwest Atlantic coast. Five fish species, namely wegde sole (Dicologoglossa cuneata), common sole (Solea vulgaris), white seabream (Diplodus sargus), sardine (Sardina pilchardus), angler fish (Lophius piscatorius), two shellfish species (Donax trunculus and Chamelea gallina), common cuttlefish (Sepia officinalis) and prawns (Parapenaeus longirostris), frequently found and consumed in the area were analysed. Concentrations ranged from 861 to 23787pg/g wet weight for total PCBs, while 2,3,7,8-PCDD/Fs showed concentrations ranging from 0.2 to 1.18pg/g wet weight. WHO-TEQ concentrations ranged from 0.038 to 0.186pg WHO-TEQ(PCDD/Fs)/g wet weight, values well below the maximum concentrations established by the EU. When non- and mono-ortho PCBs were included the values increased to a maximum of 0.99pg WHO-TEQ(PCDD/Fs+PCBs)/g wet weight. The PCB and PCDD/F accumulation pattern found in the samples analysed showed a distribution typically reported for marine samples, and no remarkable differences were found between species. The PCBs were the ones contributing with the highest percentage to the total TEQ content in most species studied. Concerning the seafood, specially prawns and shellfish, the opposite was observed and PCDD/Fs were found to contribute with a higher percentage than PCBs. The congener specific contribution to the TEQ showed PCB 126 followed by 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF as the most abundant ones.     

Disposition of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in two Norwegian epibenthic marine food webs

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of halogenated hydrocarbons, comprising 210 different, theoretically possible congeners. They are relatively hydrophobic and persistent to biodegradation, thereby rendering them subject to bioaccumulation. This study was conducted in Frierfjord and Eidangerfjord in the Grenland fjord system, Norway, heavily polluted by PCDD/PCDF discharges from the magnesium production at Herøya from 1951 to 2001. Pooled samples of surface-sediments and the following organisms were collected for the Frierfjord and Eidangerfjord study areas: common shrimp (Crangon crangon), polychaetes (mainly Nereis diversicolor), shore crab (Carcinus maenas), cod (Gadus morhua), flounder (Platichthys flesus), trout (Salmo trutta), herring (Clupea harengus), benthic amphipods and zooplankton. Concentrations of 2,3,7,8-PCDD/Fs were quantified in pooled samples for all species. The relative abundances of stable isotopes of nitrogen (δ¹⁵N) were evaluated in the organisms as a measure of chemically-derived trophic level. Contrary to earlier studies on other persistent organochlorines, it was found that the concentrations of PCDD/Fs declined with increasing trophic level. Principal Component Analysis (PCA) also showed differences between species in the pattern of PCDD/Fs. Higher chlorinated congeners constituted lower percentages of the PCDD/F-concentrations higher in the food chain as compared to lower trophic levels. In general, congener patterns did not differ between fjords. Infauna (polychaetes) and zooplankton had congener patterns most similar to the pollution source. The results indicate lower accumulation of higher chlorinated congeners in species at higher trophic levels (fish), presumably due to low membrane permeability (high molecular size) and possibly slow transport through intestinal aqueous phases because of low aqueous solubility.     

Contents and origin of polychlorinated diphenyl ethers (PCDE) in salmon from the Baltic Sea, Lake Saimaa and the Tenojoki river in Finland

The presence of 26 congeners of polychlorinated diphenyl ethers (PCDEs) was investigated in salmon from three locations in Finland. In addition to salmon, one chlorophenol wood preservative (Ky-5) and one fly ash sample were analyzed for PCDEs. Concentrations of PCDE congeners in salmon muscle measured by high resolution gas chromatography/low resolution mass spectrometry ranged from < 0.02 to 2.4 ng/g fresh weight. The major components of tetra- to octachlorinated PCDEs in salmon were one TeCDE (22′44′-), two PeCDEs (22′44′5- and 23′44′5-) and three HxCDEs (22′44′56′-, 22′44′55′- and 22′344′5-). The Baltic salmon caught from the Simojoki River had higher levels of PCDEs than the Atlantic salmon from the Tenojoki River or salmon from Lake Saimaa in South-Finland. Same PCDE congeners which were abundant in the wood preservative were also detected in salmon, whereas PCDE congeners in the fly ash were different from those in salmon or in Ky-5.