Levels and congener profiles of PBDEs in edible Baltic, freshwater, and farmed fish in Finland.

Fish is the major source of polybrominated diphenyl ethers (PBDEs) for Finnish consumers. To estimate the PBDE contamination in fish that Finns regularly consume as food, a large-scale sampling was undertaken in 2009-2010. Altogether 207 samples of 17 edible fish species were collected from commercially and recreationally important fishing areas in the Baltic Sea, freshwater lakes, and farming facilities. The analysis of 15 PBDE congeners was performed in an accredited testing laboratory with high-resolution gas chromatography mass spectrometry. In all of the samples, the Σ15PBDE varied between 0.029 and 73 ng/g fw. The most abundant congeners were BDE-47 (average proportion 42%), -99 (8.4%), -100 (11%), -154 (5.6%), and -209 (27%). High levels of BDE-209 were observed in the Baltic Sea, off the coast of Pori, in Baltic herring, perch, pike, and pike-perch. Overall, the PBDE levels in Baltic and freshwater fish were low. The levels in farmed whitefish were slightly higher than in wild whitefish. The reasons for the high BDE-209 levels in Baltic herring in Pori and the elevated levels of PBDEs in farmed whitefish should be investigated more thoroughly.

Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland.

In this study, the concentration of perfluoroalkyl acids (PFAAs) in various edible Finnish Baltic Sea, freshwater, and farmed fish species were analysed. PFAAs were present in all the Baltic and freshwater species, but were not observed in any farmed fish. The most abundant compound in each species was perfluorooctane sulfonate (PFOS), comprising 41-100% of the total concentration. The total PFAA concentration varied considerably from 0.31 to 46ngg(-1) fresh weight. A notable variation in the PFAA concentrations implies that a single fish species alone is not suitable for monitoring PFAA contamination in a certain area. Our results confirm that wild domestic fish is one of the PFAA source in the Finnish diet.

Estimated intake levels for Finnish children of methylmercury from fish.

Methylmercury (MeHg) is a well-known neurotoxic agent, and consumption of contaminated fish is the principal environmental source of MeHg exposure in humans. Children are more susceptible to adverse effects than adults. No previous specific data exist for intake by Finnish children of methylmercury from fish. We estimated fish consumption and MeHg intakes from species most commonly consumed by Finnish children aged 1-6 years. The total mercury concentrations were determined in fish species consumed, and age-specific methylmercury intakes were derived. We also examined safety margins and the proportion of children exceeding the tolerable daily intakes set by international expert bodies. The daily intake of MeHg ranged from 0 to 0.33 µg/kg bw. The strictest reference value 0.1 µg/kg bw/day for MeHg, proposed by USEPA, was exceeded by 1-15% of the study population, and FAO/WHO JECFA provisional tolerable weekly intake of 1.6 µg/kg bw was exceeded by 1% of boys and 2.5% of girls aged 6 years. Intakes of 1-year old girls were higher than of boys, whereas for 3-year olds they were the opposite. The highest intakes were observed for 6-year-old boys and girls. There was great variation in the estimated MeHg intakes among Finnish children.

Long-term daily intake estimates of polychlorinated dibenzo-p-dioxins and furans, polychlorinated biphenyls and polybrominated diphenylethers from food in Finnish children: risk assessment implications.

Food is contaminated by polychlorinated dibenzo-p-dioxins and furans (PCDD/F), polychlorinated biphenyls (PCB) and polybrominated diphenylethers (PBDE) worldwide. Previous data show elevated intakes in children. We determined intakes of POPs in Finnish children. Because no children-specific safe limit values exist, we used tolerable daily intakes (TDIs) set for adults by international expert bodies to examine the proportion of the study population that exceed those limits. We utilised dietary monitoring data with food consumption of Finnish boys and girls aged 1-6 years, measured the contaminant concentrations in all the main food items and calculated age-specific contaminant sum and congener-specific long-term daily intake levels. Our food intake and contaminant data correspond to years 2002-2005. The long-term upper-bound dioxin intakes ranged between 0.1 and 12.8 pg WHO(PCDD/F-PCB)-TEQ/kg bw/d (min and max). An immediate TDI for WHO(PCDD/F-PCB)-TEQs of 4.0 pg/kg bw/d were exceeded by 2.5%-7.5% of the children. PBDE long-term upper-bound intake was between 0.1 and 5.8 ng/kg bw/d (min and max). Congener-specific analyses indicated a typical Finnish adult exposure pattern of the children to PCDD/Fs, PCBs and PBDEs. The highest POP intakes were observed in children aged 3 years. Long-term daily PCDD/F, PCB and PBDE intakes among Finnish children varied greatly between individuals and ages. In each age group of the study population, there was a proportion of children with their WHO(PCDD/F-PCB)-TEQ intake exceeding considered safe limits set for adults. Based on the exposure profile reported herein, children should be clearly considered as a specific sub-population in food-mediated contaminant risk assessment.

210Pb and 210Po in Finnish cereals.

A survey was carried out on the activity concentrations of (210)Pb and (210)Po in cereal grains produced in Finland. The cereal species were wheat (Triticum aestivum), rye (Secale cereale), oats (Avena sativa) and barley (Hordeum vulgare), which account for 90% of the Finnish consumption of cereal products. The survey consisted of 18 flour and 13 unprocessed cereal samples and one hulled grain sample from 22 flour mills. According to the results, the mean (210)Pb/(210)Po concentrations in wheat grains, wheat flour, rye flour, oat grains and barley grains were 0.29, 0.12, 0.29, 0.36 and 0.36 Bq kg(-1), respectively. Combined with the consumption rates of the products, we assess that the mean effective doses from (210)Pb and (210)Po in cereal products for the adult male and female population are 22 and 17 µSv per year, respectively.

Organotin intake through fish consumption in Finland.

BACKGROUND: Organotin compounds (OTCs) are a large class of synthetic chemicals with widely varying properties. Due to their potential adverse health effects, their use has been restricted in many countries. Humans are exposed to OTCs mostly through fish consumption. OBJECTIVES: The aim of this study was to describe OTC exposure through fish consumption and to assess the associated potential health risks in a Finnish population. METHODS: An extensive sampling of Finnish domestic fish was carried out in the Baltic Sea and freshwater areas in 2005-2007. In addition, samples of imported seafood were collected in 2008. The chemical analysis was performed in an accredited testing laboratory during 2005-2008. Average daily intake of the sum of dibutyltin (DBT), tributyltin (TBT), triphenyltin (TPhT) and dioctyltin (DOT) (SigmaOTCs) for the Finnish population was calculated on the basis of the measured concentrations and fish consumption rates. RESULTS: The average daily intake of SigmaOTCs through fish consumption was 3.2ng/kgbwday(-1), which is 1.3% from the Tolerable Daily Intake (TDI) of 250ng/kgbwday(-1) set by the European Food Safety Authority. In total, domestic wild fish accounted for 61% of the SigmaOTC intake, while the intake through domestic farmed fish was 4.0% and the intake through imported fish was 35%. The most important species were domestic perch and imported salmon and rainbow trout. CONCLUSIONS: The Finnish consumers are not likely to exceed the threshold level for adverse health effects due to OTC intake through fish consumption.

Modelling the intake of polychlorinated dibenzo-p-dioxins and dibenzofurans: impact of energy under-reporting and number of reporting days in dietary surveys.

A probabilistic long-term intake estimation of dioxins was carried out using food consumption data obtained from the National FINDIET 2007 Survey (Paturi et al. 2008). The study population consisted of 606 participants who were first interviewed with a 48-h recall and then filled in a 3-day food record twice. The concentrations of dioxins were obtained from previously published studies. The intake was estimated using a semi-parametric Monte Carlo simulation. The analyses were done separately for the whole study population and for the population excluding energy under-reporters. To diminish the impact of intra-individual variation and nuisance effects, adjustment with software (C-SIDE) was also done after Monte Carlo simulation. It was found that when C-SIDE was used, the 95th percentile of intake and its confidence limit was higher with 2 reporting days than with a higher number of days. However, with a crude intake estimation (no adjustment), the confidence intervals of the 95th percentile were also smaller with a higher number of days, but the 95th percentiles were higher with a higher number of reporting days. When under-reporters were excluded the intakes increased, but the impact of energy under-reporting was smaller with 8 reporting days than with 2 days and smaller using C-SIDE than with a crude estimation. To conclude, adjustment for intra-individual variation and taking energy under-reporting into account are essential for intake estimation of dioxins with food consumption data of a limited number of reporting days.

Concentrations of organotin compounds in various fish species in the Finnish lake waters and Finnish coast of the Baltic Sea.

Organotin compounds (OTCs) leaching from the antifouling paints used in boats and ships have contaminated many water areas worldwide. The purpose of this study was to obtain a general view of the organotin contamination in fish in Finnish lake areas and Finnish coast of the Baltic Sea using perch as the main indicator species. Perch sampling covered areas presumed as less contaminated and areas suspected as more contaminated. Besides perch, 12 other species were sampled from sites presumed as less contaminated. OTCs measured were mono-, di- and tributyltin, mono-, di-, and triphenyltin and dioctyltin. The sum concentration of OTCs (SigmaOTCs) in perch in the least contaminated areas of the Baltic Sea were around 20 ng/g fresh weight (fw) and less than 10 ng/g fw in lake areas. In heavily contaminated areas of the Baltic Sea 150-500 ng/g fw in perch were detected. In lake areas the maximum SigmaOTCs in perch was only 30 ng/g fw. With regard to the other species in the Baltic Sea, salmon, sprat, flounder, whitefish, vendace and lamprey contained low concentrations (SigmaOTCs mainly less than 20 ng/g fw), whereas in pike, pike-perch, burbot and bream concentrations were higher. SigmaOTCs in lake fish were generally lower than in the Baltic Sea. In a distance gradient study, SigmaOTCs in perch decreased quickly from nearly 200 ng/g fw at a contaminated harbor area to 35 ng/g fw during a distance of 5 km. Further decrease was slower and reached 15 ng/g fw at 100 km. In a size dependence study triphenyltin showed better correlation with the fish length than tributyltin for all species studied, i.e. for perch (0.16 vs 0.26), pike-perch (0.13 vs 0.24) and roach (0.46 vs 0.80). High correlation for roach may be partly explained by smaller number of samples collected and small length range.

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls in semi-domesticated reindeer (Rangifer tarandus tarandus) and wild moose (Alces alces) meat in Finland.

Semi-domesticated reindeer and wild moose meat samples were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs). Both calves and adults were studied. Individual reindeer and moose meat samples and pooled reindeer calf meat samples were collected from the northern, the middle, and the southern reindeer herding regions in Finland. Samples represented the edible parts of carcasses. In individual samples of reindeer the fat based WHO-PCDD/F-PCB-TEQ concentration was on average 3.2pgg(-1) in calves and 2.3pgg(-1) in adults. In moose calves the fat based WHO-PCDD/F-PCB-TEQ concentration (1.9pgg(-1)) was lower than in reindeer calves. WHO-PCDD/F-PCB-TEQ concentration in the adult moose samples was equal as in the adult reindeer samples. The mean fat based WHO-PCDD/F-PCB-TEQ concentration was highest in reindeer calf samples from the middle region. These samples contained also the highest content of fat. Individual samples of reindeer contained on average more WHO-PCB-TEQ than WHO-PCDD/F-TEQ, while the opposite was true for moose samples, and also samples of adult reindeer from the southern area. The contributions of PCDD/Fs and PCBs to the total TEQ were similar in the reindeer calves' pooled samples which were collected from more western regions than individual samples.

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors.

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.

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.

Acrylamide levels in Finnish foodstuffs analysed with liquid chromatography tandem mass spectrometry.

Sample clean-up and HPLC with tandem mass spectrometric detection (LC-MS/MS) was validated for the routine analysis of acrylamide in various foodstuffs. The method used proved to be reliable and the detection limit for routine monitoring was sensitive enough for foods and drinks (38 microg/kg for foods and 5 microg/L for drinks). The RSDs for repeatability and day-to-day variation were below 15% in all food matrices. Two hundred and one samples which included more than 30 different types of food and foods manufactured and prepared in various ways were analysed. The main types of food analysed were potato and cereal-based foods, processed foods (pizza, minced beef meat, meat balls, chicken nuggets, potato-ham casserole and fried bacon) and coffee. Acrylamide was detected at levels, ranging from nondetectable to 1480 microg/kg level in solid food, with crisp bread exhibiting the highest levels. In drinks, the highest value (29 microg/L) was found in regular coffee drinks.

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.

The dependence of organohalogen compound concentrations on herring age and size in the Bothnian Sea, northern Baltic.

The concentrations and composition profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls, polybrominated diphenyl ethers and polychlorinated naphthalenes were determined in herring individuals collected from the commercial catches of the Bothnian Sea, northern Baltic. The median age of herring was 5.0 years and in the muscle the median toxic equivalent concentration of PCDD/Fs was 5.6 WHO(PCDD/F)-TEQ pg/g fresh weight (fw) and that of PCBs 2.7 WHO(PCB)-TEQ pg/g fw. The median sum concentration of PBDEs was 1.4 ng/g fw and that of PCNs 0.1 ng/g fw. Differences in age-dependent accumulation between the organohalogen groups and individual congeners were major. In the Bothnian Sea the content of organohalogen compounds in herring is obviously elevated due to the availability and large proportion of Mysis crustaceans in their diet. More intensive fishing could reduce the concentrations of organohalogens, including the abundant, accumulative and toxic 2,3,4,7,8-PeCDF congener in the Baltic herring catch.

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.

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.