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.

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.

Detecting AhR ligands in sediments using bioluminescent reporter yeast.

Sediments polluted with high concentrations of persistent organic pollutants, many of which are ligands of the aryl hydrocarbon receptor (AhR), are currently of concern around the industrialized world. Bioassays that can detect the presence of AhR ligands in environmental samples offer a relatively rapid and cost-effective means of prioritizing samples before more elaborate, laborious, and costly chemical analyses are applied. This paper presents a new bioluminescent yeast assay based on transcriptional activation of AhR. Its applicability for determining AhR ligands in complex environmental samples was demonstrated by analyzing a set of sediment samples from the River Kymi, Finland. The results from the assay are shown to be consistent with those from both a chemical analysis and an H4IIE-luc bioassay. The yeast assay procedure is simple and can be performed within 1 day. The yeasts grow rapidly, are easy to handle, and do not require continuous cell culturing. Moreover, the robustness of the yeast allows the application of the test to crude extracts or even sediment suspensions. The yeast assay described in this paper can be useful in screening and prioritization of samples prior to chemical analysis. Moreover, the strain can be used in the construction of fibre-optic biosensors.

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.

Modeling the transport of PCDD/F compounds in a contaminated river and the possible influence of restoration dredging on calculated fluxes.

River Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as by chemical industry. Loading has been reduced considerably, although remains of past emissions still exist in river sediments. The sediments are highly contaminated with polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated diphenyl ethers (PCDEs), and mercury originating from production of the chlorophenolic wood preservative (Ky-5) and other sources. The objective of this study was to simulate the transport of these PCDD/F compounds with a one-dimensional flow and transport model and to assess the impact of restoration dredging. Using the estimated trend in PCDD/F loading, downstream concentrations were calculated until 2020. If contaminated sediments are removed by dredging, the temporary increase of PCDD/F concentrations in downstream water and surface sediments will be within acceptable limits. Long-term predictions indicated only a minor decrease in surface sediment concentrations but a major decrease if the most contaminated sediments close to the emission source were removed. A more detailed assessment of the effects is suggested.

Spatial distibution and temporal accumulation of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in the Gulf of Finland.

Dated sediment cores and surface sediments were analyzed from the Gulf of Finland, a part of the Baltic Sea, to study the sources, levels, distribution, and total amounts of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). The gulf was found to be severely polluted, with PCDD/F sum concentrations as high as 101000 ng/kg and 479 ng/kg WHO-TEQ in dry weight. The source of pollution was the former manufacturing and use of a chlorophenol based wood preservative along the Kymijoki River. It was estimated thatthe impacted sedimentary area stretched a distance of 75 km away out from the coast and that the PCDD/F sum load attributed to the wood preservative source was 1770 kg of PCDD/Fs or 12.4 (+/-2.8) kg WHO-TEQ. The surface sediments contained 24-66% of the maximum concentrations present in the 1960-1970s, showing that the river still acts as a significant PCDD/F source and may contribute to the high levels in fish. Moreover, the reduced PCDD/F and PCB concentrations were partly due to the dilution by increased dry matter deposition. PCBs were uniformly distributed over the gulf, and the PCB load in the polluted area was 2020 kg or 0.14 kg WHO-TEG.