PCDD/Fs, PCBs and PBDEs in zooplankton in the Baltic Sea - spatial and temporal shifts in the congener-specific concentrations.

In the marine food-webs, zooplankton is a key element in the transfer of persistent organic pollutants to higher trophic levels. We determined the congener-specific concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in offshore zooplankton (size from 0.2 to 20mm) collected in 2001, 2002 and 2010 in the northern and central Baltic Sea. Of the PCDD/Fs, the concentrations of 2378-TCDF were from 18 to 47 and of 23478-PeCDF from 7.9 to 29 pg g(-1)fat and showed little temporal differences. However, 1234678-HpCDF and OCDF were abundant in 2001-2002 especially in the eastern Gulf of Finland (average concentrations 50 and 89 pg g(-1)fat, respectively). In 2010 the concentrations of these two congeners were lower, 29 and 30 pg g(-1)fat, respectively, but still substantially higher than in the other surveyed areas. The principal components analysis (PCA) supported that area-specific patterns in pollution strongly contributed to the congener profiles particularly in surface sediment and in sediment trap material, but even in zooplankton. The concentrations of the PCBs were highest in the Gulf of Finland and in the Bothnian Bay. The concentrations of most PCBs were somewhat lower in 2010 than in 2001-2002. Of the dioxin-like PCBs, the concentrations of PCB-77 were highest (271-572 pg g(-1)fat) but PCB-126 (32-113 pg g(-1)fat) contributed from 85% to 91% of the total toxicity of PCBs due to its higher toxic potency. Of the PBDEs, the BDE47 and BDE99 were the most abundant (concentrations from 1.2 to 4.6 and from 0.4 to 3.3 ng g(-1) fat, respectively). The concentrations of most PBDEs were lower in 2010 than in 2001/2002 except in the eastern Gulf of Finland.

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.

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.

Climate induced thermocline change has an effect on the methyl mercury cycle in small boreal lakes.

We conducted a whole-lake experiment by manipulating the stratification pattern (thermocline depth) of a small polyhumic, boreal lake (Halsjärvi) in southern Finland and studying the impacts on lake mercury chemistry. The experimental lake was compared to a nearby reference site (Valkea-Kotinen Lake). During the first phase of the experiment the thermocline of Halsjärvi was lowered in order to simulate the estimated increase in wind speed and in total lake heat content (high-change climate scenario). The rate of methyl mercury (MeHg) production during summer stagnation (May-August) was calculated from water profiles before the treatment (2004), during treatment (2005, 2006) and after treatment (2007). We also calculated fluxes of MeHg from the epilimnion and from the hypolimnion to the sediments using sediment traps. Experimental mixing with a submerged propeller caused a 1.5-2 m deepening of the thermocline and oxycline. Methyl mercury production occurred mostly in the oxygen free layers in both lakes. In the experimental lake there was no net increase in MeHg during the experiment and following year; whereas the reference lake showed net production for all years. We conclude that the new exposed epilimnetic sediments caused by a lowering of the thermocline were a major sink for MeHg in the epilimnion. The results demonstrate that in-lake MeHg production can be manipulated in small lakes with anoxic hypolimnia during summer. The climate change induced changes in small boreal lakes most probably affect methyl mercury production and depend on the lake characteristics and stratification pattern. The results support the hypothesis that possible oxygen related changes caused by climate change are more important than possible temperature changes in small polyhumic lakes with regularly occurring oxygen deficiency in the hypolimnion.

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 5x10(6) 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 mug 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.

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.

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.