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.

Microbially mediated reductive dechlorination of weathered polychlorinated dibenzofurans in Kymijoki sediment mesocosms.

Little is known about the potential for indigenous microorganisms to reductively dechlorinate weathered polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in contaminated sediments. The sediments of River Kymijoki, Finland are heavily contaminated with PCDFs originating from manufacture of the chlorophenol-based fungicide Ky-5. Reductive dechlorination of weathered PCDFs was monitored to examine strategies for stimulating such activities. Amendments with electron donors, a halogenated co-substrate (tetrachlorobenzene, TeCBz), and bioaugmentation with a mixed culture containing Dehalococcoides mccartyi strain 195 were used to stimulate dechlorination activity in 30 L River Kymijoki sediment mesocosms incubated from 18 °C to 21 °C. An initial onset of dechlorination of octa-, hepta- and hexa-CDFs was observed in all mesocosms in the first 2 years of incubation. During this initial 2-year period, the decrease in the mol% contribution of these PCDFs was coupled with an increase in the mol% contribution of tetra- and penta-CDFs. The ratio of 1,2,3,4,6,7,8- to 1,2,3,4,6,8,9-hepta-CDF increased significantly. Subtle differences were observed between amended and unamended mesocosms. For penta-CDFs, a decreasing mol% ratio of peri vs. total chlorines and increasing mol% ratio of lateral vs. total chlorines was observed in mesocosms amended with TeCBz, suggesting that the amendments may affect pathways of dechlorination. Analysis of congener patterns using principal components analysis supported the observation that dechlorination was most pronounced during the first 2 years. Polymerase chain reaction and denaturing gradient gel electrophoresis (PCR-DGGE) analysis of 16S rRNA genes revealed a diverse Chloroflexi community. This study showed evidence for dechlorination of weathered PCDFs in Kymijoki sediment mesocosms mediated by indigenous microorganisms.

Biomagnification of organohalogens in Atlantic salmon (Salmo salar) from its main prey species in three areas of the Baltic Sea.

Factors affecting the biomagnification of organohalogens in Baltic salmon from sprat, herring and three-spined stickleback were assessed in three feeding areas. Second sea-year salmon contained (in fresh weight of whole fish) 79-250ngg(-1) polychlorinated biphenyls (ΣPCB), 0.9-2.7pgg(-1) dibenzo-p-dioxins (ΣPCDD), 8-19pgg(-1) dibenzofurans (ΣPCDF), 96-246pgg(-1) coplanar PCBs, 2.4-3.6ngg(-1) polybrominated diphenylethers (ΣPBDE), and 39-136ngg(-1) Σ(indicator) PCB6. The EU limits for WHO toxic equivalent concentrations in fish feed were already exceeded in one-year-old sprat and herring and were exceeded many-fold in older age groups. The differences in the biomagnification rates of organohalogens in salmon appeared to be related to the feeding area, principal prey species, and the fat content and growth rate of the prey species.

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.

Trophodynamics of mercury and other trace elements in a pelagic food chain from the Baltic Sea.

Mercury (Hg) and 13 other trace elements (Al, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Cd, and Pb) were measured in phytoplankton, zooplankton, mysis and herring in order to examine the trophodynamics in a well-studied pelagic food chain in the Baltic Sea. The fractionation of nitrogen isotopes (delta(15)N) was used to evaluate food web structure and to estimate the extent of trophic biomagnification of the various trace elements. Trophic magnification factors (TMFs) for each trace element were determined from the slope of the regression between trace element concentrations and delta(15)N. Calculated TMFs showed fundamental differences in the trophodynamics of the trace elements in the pelagic food chain studied. Concentrations of Al, Fe, Ni, Zn, Pb and Cd showed statistically significant decreases (TMF<1) with increasing trophic levels and thus these trace elements tropically dilute or biodilute in this Baltic food chain. Cu, As, Cr, Mn, V, Ti and Co showed no significant relationships with trophic levels. Hg was unique among the trace elements studied in demonstrating a statistically significant increase (TMF>1) in concentration with trophic level i.e. Hg biomagnifies in this Baltic food chain. The estimated TMF for Hg in this food chain was comparable to TMFs observed elsewhere for diverse food chains and locations.

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.

Modeling the importance of biota and black carbon as vectors of polybrominated diphenyl ethers (PBDEs) in the Baltic Sea ecosystem.

The POPCYCLING-Baltic model, a nonsteady state spatially resolved mass balance model of chemical transport in the Baltic Sea environment was modified to include black carbon (BC), dissolved organic carbon (DOC) and food-web bioaccumulation. The importance of these modifications to the transport of PBDE congeners BDE-47, -99, -153, and -209 was assessed by comparing time-series simulated with and without black carbon and biota between 1970 and 2005. Inclusion of black carbon improved the model fit to measurements from air, soil, and biota, and had a major effect on the mass balance. Modeled bulk concentrations of PBDEs in sediments and soils increased by a factor of 3 while concentrations in biota decreased by a factor of 2-5. Black carbon also doubled the recovery time of the system due to the limited availability of PBDEs for degradation. In comparison, the inclusion of biota had only a minor effect on the overall mass balance and recovery times. The modified model is constructed as a flexible matrix and can also be applied to persistent organic pollutants in other ecosystems besides the Baltic Sea.

Dioxin- and POP-contaminated sites--contemporary and future relevance and challenges: overview on background, aims and scope of the series.

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.

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.

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.

Interference of contaminated sediment extracts and environmental pollutants with retinoid signaling.

Retinoids are known to regulate important processes such as differentiation, development, and embryogenesis. Some effects, such as malformations in frogs or changes in metabolism of birds, could be related to disruption of the retinoid signaling pathway by exposure to organic contaminants. A new reporter gene assay has been established for evaluation of the modulation of retinoid signaling by individual chemicals or environmental samples. The bioassay is based on the pluripotent embryonic carcinoma cell line P19 stably transfected with the firefly luciferase gene under the control of a retinoic acid-responsive element (clone P19/ A15). The cell line was used to characterize the effects of individual chemicals and sediments extracts on retinoid signaling pathways. The extracts of sediments from the River Kymi, Finland, which contained polychlorinated dioxins and furans and polycyclic aromatic hydrocarbons (PAHs), significantly increased the potency of all-trans retinoic acid (ATRA), while no effect was observed with the extract of the sediment from reference locality. Considerable part of the effect was caused by the labile fraction of the sediment extracts. Also, several individual PAHs potentiated the effect of ATRA; on the other hand, 2,3,7,8-tetrachlorodibenzo-p-dioxin and several phthalates showed slightly inhibiting effect. These results suggest that PAHs could be able to modulate the retinoid signaling pathway and that they could be responsible for a part of the proretinoid activity observed in the sediment extracts. However, the effects of PAHs on the retinoic acid signaling pathways do not seem to be mediated directly by crosstalk with aryl hydrocarbon receptor.

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.

Predicting effects of exploitation rate on weight-at-age, population dynamics, and bioaccumulation of PCDD/Fs and PCBs in herring (Clupea harengus L.) in the Northern Baltic Sea.

The Baltic Sea ecosystem and fish stocks contain high concentrations of environmental chemicals such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs). This study forecasts how changes in fishing or natural mortality would probably influence concentrations of PCDD/F and PCB in the Bothnian Sea (Northern Baltic) herring (Clupea harengus L.). An age-structured simulation model was developed to forecast herring stock dynamics, catches, and weight-at-age under different assumptions about exploitation and natural mortality. The simulated herring weight-at-age estimates were employed in a bioenergetics model capable of simultaneous estimation of bioaccumulation of 17 PCDD/F and 37 PCB congeners. Although the natural variability in recruitment greatly influences the stock dynamics, considerable changes in weight-at-age would ensue changes in exploitation rate or in natural mortality rate. If exploitation rates increase, growth rates would be higher and herring in the weight categories of commercial fisheries would be younger and contain less PCDD/F and PCB. Hence, the average toxicant concentrations in catches would also decline. However, it is likely that only fairly small changes would occur in toxicant concentrations-at-age. On the other hand, a drastic decrease in herring fishing would substantially increase PCDD/F and PCB concentrations in herring. The study indicated that, in spite of the clear influences of fishing on the toxicant concentrations, fishing alone cannot resolve the problems associated with a high concentration of toxicants in herring; further decreases in loading are still required.

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.

Forestry practices increase mercury and methyl mercury output from boreal forest catchments.

We observed significant increases in the runoff output of total mercury (TotHg) and methyl mercury (MeHg) from a small spruce forest catchment (0.071 km2) after clear-cutting and soil treatment. Here we show that forest regeneration practices may act as an important additional source of TotHg and MeHg to forest lakes. TotHg and MeHg in runoff from two small forested catchments were monitored during the period 1994 to 2001. In the autumn of 1997, one of the catchments was clear-cut Soil preparation (mounding) was carried out in the autumn of 1998 and replanting in the summer of 1999. During the 3 years after the silvicultural treatment, medians of monthly flow-weighted TotHg and MeHg concentrations (12.02 ng L(-1) and 0.35 ng L(-1), respectively) and output loads (0.80-0.97 g km(-2) a(-1) and 0.011-0.036 g km(-2) a(-1), respectively) increased significantly compared to the 3 years calibration period (8.13 ng L(-1) and 0.15 ng 1(-1); 2.0-5.3 g km(-2) a(-1) and 0.11-0.16 g km(-2) a(-1), respectively). These results indicate that clear-cutting and/or soil treatment significantly increases the mobility of TotHg and MeHg accumulated in forest soil and may thus be an important factor for the total input of Hg to boreal freshwater ecosystems.

Total and methyl mercury concentrations and fluxes from small boreal forest catchments in Finland.

Total mercury (TotHg) and methyl mercury (MeHg) concentrations were studied in runoff from eight small (0.02-1.3 km2) boreal forest catchments (mineral soil and peatland) during 1990-1995. Runoff waters were extremely humic (TOC 7-70 mg l-1). TotHg concentrations varied between 0.84 and 24 ng l-1 and MeHg between 0.03 and 3.8 ng l-1. TotHg fluxes from catchments ranged from 0.92 to 1.8 g km-2 a-1, and MeHg fluxes from 0.03 to 0.33 g km-2 a-1. TotHg concentrations and output fluxes measured in runoff water from small forest catchments in Finland were comparable with those measured in other boreal regions. By contrast, MeHg concentrations were generally higher. Estimates for MeHg output fluxes in this study were comparable at sites with forests and wetlands in Sweden and North America, but clearly higher than those measured at upland or agricultural sites in other studies. Peatland catchments released more MeHg than pure mineral soil or mineral soil catchments with minor area of peatland.