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.     

Spatial variation in soil carbon in the organic layer of managed boreal forest soil—implications for sampling design

We studied within-site spatial variation of the carbon stock in the organic layer of boreal forest soil. A total of 1,006 soil samples were taken in ten forest stands (five Scots pine stands and five Norway spruce stands). Our results indicate that the spatial autocorrelation disappears at a distance of 75-225 cm. This spatial autocorrelation should be taken into account in the sampling design by locating the sampling points at adequate intervals. With a sample size of over 20-30 samples per site, additional soil samples do not notably improve the precision of the site mean estimate. An adequate sample size is dependent on the purpose of sampling and on the site-specific soil variation. Our results on the dependence between sample size and precision of the mean estimates can be applied in designing efficient soil monitoring in boreal coniferous forests.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Educating the next generation of atmospheric scientists within a European Network of Excellence

In order to promote the next generation of atmospheric scientists, the task Training and Education (T&E) in ACCENT, the European Network of Excellence in Atmospheric Composition Change (www.accent-network.org) has developed and implemented an Integrated Learning Environment (ILE). For school teachers and their students, the Internet-based “Global Change Magazine” provides up-to-date and freely accessible scientific material in English and five other languages. Additionally, T&E has produced online teaching material for early-career scientists. These e-learning modules are now being used in University Master's courses across Europe. T&E also organised training events for early-career scientists, combining scientific content with development in transferable skills, to focus on interdisciplinary collaboration, interaction with senior scientists, communication with stakeholders, and dissemination to the general public. Evaluation based on participant feedback evidences the effectiveness of these events, e.g., in terms of motivation to remain in the field. Methodologies and materials from T&E are being published in a Handbook on Best Practice, intended for both educators and scientists around the globe who are involved in education in the field of air quality and climate change science.     

Activated carbon amendment to sequester PAHs in contaminated soil: a lysimeter field trial

Activated carbon (AC) amendment is an innovative method for the in situ remediation of contaminated soils. A field-scale AC amendment of either 2% powder or granular AC (PAC and GAC) to a PAH contaminated soil was carried out in Norway. The PAH concentration in drainage water from the field plot was measured with a direct solvent extraction and by deploying polyoxymethylene (POM) passive samplers. In addition, POM samplers were dug directly in the AC amended and unamended soil in order to monitor the reduction in free aqueous PAH concentrations in the soil pore water. The total PAH concentration in the drainage water, measured by direct solvent extraction of the water, was reduced by 14% for the PAC amendment and by 59% for GAC, 12 months after amendment. Measurements carried out with POM showed a reduction of 93% for PAC and 56% for GAC. The free aqueous PAH concentration in soil pore water was reduced 93% and 76%, 17 and 28 months after PAC amendment, compared to 84% and 69% for GAC. PAC, in contrast to GAC, was more effective for reducing freely dissolved concentrations than total dissolved ones. This could tentatively be explained by leaching of microscopic AC particles from PAC. Secondary chemical effects of the AC amendment were monitored by considering concentration changes in dissolved organic carbon (DOC) and nutrients. DOC was bound by AC, while the concentrations of nutrients (NO(3), NO(2), NH(4), PO(4), P-total, K, Ca and Mg) were variable and likely affected by external environmental factors.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

An integrated approach to model the biomagnification of organic pollutants in aquatic food webs of the Yangtze Three Gorges Reservoir ecosystem using adapted pollution scenarios

The impounding of the Three Gorges Reservoir (TGR) at the Yangtze River caused large flooding of urban, industrial, and agricultural areas, and profound land use changes took place. Consequently, substantial amounts of organic and inorganic pollutants were released into the reservoir. Additionally, contaminants and nutrients are entering the reservoir by drift, drainage, and runoff from adjacent agricultural areas as well as from sewage of industry, aquacultures, and households. The main aim of the presented research project is a deeper understanding of the processes that determines the bioaccumulation and biomagnification of organic pollutants, i.e., mainly pesticides, in aquatic food webs under the newly developing conditions of the TGR. The project is part of the Yangtze-Hydro environmental program, financed by the German Ministry of Education and Science. In order to test combinations of environmental factors like nutrients and pollution, we use an integrated modeling approach to study the potential accumulation and biomagnification. We describe the integrative modeling approach and the consecutive adaption of the AQUATOX model, used as modeling framework for ecological risk assessment. As a starting point, pre-calibrated simulations were adapted to Yangtze-specific conditions (regionalization). Two exemplary food webs were developed by a thorough review of the pertinent literature. The first typical for the flowing conditions of the original Yangtze River and the Daning River near the city of Wushan, and the second for the stagnant reservoir characteristics of the aforementioned region that is marked by an intermediate between lake and large river communities of aquatic organisms. In close cooperation with German and Chinese partners of the Yangtze-Hydro Research Association, other site-specific parameters were estimated. The MINIBAT project contributed to the calibration of physicochemical and bathymetric parameters, and the TRANSMIC project delivered hydrodynamic models for water volume and flow velocity conditions. The research questions were firstly focused on the definition of scenarios that could depict representative situations regarding food webs, pollution, and flow conditions in the TGR. The food webs and the abiotic site conditions in the main study area near the city of Wushan that determine the environmental preconditions for the organisms were defined. In our conceptual approach, we used the pesticide propanil as a model substance.     

A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.     

The Effects of Hypoxia on Sediment Nitrogen Cycling in the Baltic Sea

Primary production in the eutrophic Baltic Sea is limited by nitrogen availability; hence denitrification (natural transformation of nitrate to gaseous N₂) in the sediments is crucial in mitigating the effects of eutrophication. This study shows that dissimilatory nitrate reduction to ammonium (DNRA) process, where nitrogen is not removed but instead recycled in the system, dominates nitrate reduction in low oxygen conditions (O₂ <110 μM), which have been persistent in the central Gulf of Finland during the past decade. The nitrogen removal rates measured in this study show that nitrogen removal has decreased in the Gulf of Finland compared to rates measured in mid-1990s and the decrease is most likely caused by the increased bottom water hypoxia.     

Quantifying the effects of trampling and habitat edges on forest understory vegetation – A field experiment

We investigated the effects of human trampling on boreal forest understory vegetation on, and off paths from suburban forest edges towards the interiors and on the likelihood of trampling-aided dispersal into the forests for three years by carrying out a trampling experiment. We showed that the vegetation was highly sensitive to trampling. Even low levels of trampling considerably decreased covers of the most abundant species on the paths. Cover decreased between 10 and 30% on paths which had been trampled 35 times, and at least by 50% on those trampled 70–270 times. On-path vegetation cover decreased similarly at forest edges and in the interiors. However, some open habitat plant species that occurred outside the forest patches and at forest edges dispersed into the forests, possibly through the action of trampling. A higher cover percentage of an open habitat species at the forest edge line increased its probability to disperse into the forest interior. The vegetation community on, next to, and away from lightly trampled paths remained the same throughout the trampling experiment. For heavily trampled paths, the community changed drastically on the paths, but stayed relatively similar next to and away from the paths. As boreal vegetation is highly sensitive to the effects of trampling, overall ease of access throughout the forest floor should be restricted to avoid the excessive creation of spontaneous paths. To minimize the effects of trampling, recreational use could be guided to the maintained path network in heavily used areas.