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 riverine nutrient transport to the Baltic Sea: a large-scale approach

We developed for the first time a catchment model simulating simultaneously the nutrient land-sea fluxes from all 105 major watersheds within the Baltic Sea drainage area. A consistent modeling approach to all these major watersheds, i.e., a consistent handling of water fluxes (hydrological simulations) and loading functions (emission data), will facilitate a comparison of riverine nutrient transport between Baltic Sea subbasins that differ substantially. Hot spots of riverine emissions, such as from the rivers Vistula, Oder, and Daugava or from the Danish coast, can be easily demonstrated and the comparison between these hot spots, and the relatively unperturbed rivers in the northern catchments show decisionmakers where remedial actions are most effective to improve the environmental state of the Baltic Sea, and, secondly, what percentage reduction of riverine nutrient loads is possible. The relative difference between measured and simulated fluxes during the validation period was generally small. The cumulative deviation (i.e., relative bias) [Sigma(Simulated - Measured)/Sigma Measured x 100 (%)] from monitored water and nutrient fluxes amounted to +8.2% for runoff, to -2.4% for dissolved inorganic nitrogen, to +5.1% for total nitrogen, to +13% for dissolved inorganic phosphorus and to +19% for total phosphorus. Moreover, the model suggests that point sources for total phosphorus compiled by existing pollution load compilations are underestimated because of inconsistencies in calculating effluent loads from municipalities.     

Environmental hazard screening of a metal-polluted site using pressurized liquid extraction and two in vitro bioassays

Rapid screening methods can improve the cost effectiveness, throughput, and quality of risk assessments of contaminated sites. In the present case study, the objective was to evaluate a combination of pressurized liquid extraction and 2 in vitro bioassays for the hazard assessment of surface soil sampled from 46 points across a pyrotechnical industrial site. Pressurized liquid extraction was used to rapidly produce soil-water extracts compatible with 2 high-capacity bioassays. Hazard assessment using combined toxicological and chemical screening revealed zones with relatively high potential risks of metal pollution. Multivariate data analysis provided indications that significant inhibition in the bioassays was correlated with levels of metals in the extracts, suggesting an elevated toxic potential from certain metals. Low pH and high concentrations of dissolved organic carbon were associated with increased cytotoxicity of extracts, indicating that these factors influence metal bioavailability. The cytotoxicity observed was more strongly correlated to metal concentrations in the extracts than in the soil, suggesting that measurements of total metal concentrations in soils do not provide good indications of the soil's potential toxicity.     

Partitioning of chloroaromatic compounds between the aqueous phase and dissolved and particulate soil organic matter at chlorophenol contaminated sites

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo-p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ~ PCDE ~ PCDF < PCDD. Differences in partitioning to DOM (logK(DOC)) and POM (logK(POC)) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of logK(POC) of 0.5 units for CPs and PCDDs. We conclude that logK(OC) for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.     

Dense resistivity and induced polarization profiling for a landfill restoration project at H?rl?v, Southern Sweden.

A resistivity and time-domain induced polarization (IP) survey was conducted at a landfill site under restoration at H?rl?v in Southern Sweden. The covering of the landfill had begun some years ago, without keeping precise records of the work done, as is usual in such procedures. The survey was conducted in two steps, on two adjacent areas. First, a number of geoelectrical sections were made on a partly covered area that had been investigated earlier by auger drilling, in order to assist restoration. Then, a second area that should have received its final cover was imaged, and some defects in the cover could be detected and repaired. The resistivity and time-domain IP results were consistent with the results of the geotechnical drillings, and they enabled quasi-continuous mapping along the profiles. Three-dimensional visualization showed the overall consistency of the two-dimensional lines, and helped to generate a global view of the site. In spite of some ambiguities, cover and waste could be distinguished in most cases. In particular, fine-grained cover materials could be clearly distinguished from other cover materials.     

SALSA: a simulation tool to assess ecological sustainability of agricultural production

In order to assess the ecological sustainability of agricultural production systems, there is a need for effective tools. We describe an environmental systems analysis tool called SALSA (Systems Ana/ysis for Sustainable Agriculture). It consists of substance/material flow models in which the simulation results are interpreted with life-cycle assessment methodology. The application of SALSA is demonstrated in a case study in which three different ways of producing pigs are compared with respect to energy input and the environmental impacts of global warming, eutrophication, and acidification. The scenario that combined a low-protein diet without soy meal with an improved manure-management technique with low nitrogen losses was the best for all impact categories studied. The strength of the SALSA models was their capacity to capture consequences of management options that had an influence on several processes on a farm, which enabled the type of complex studies we describe.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

Evaluation criteria for AIS 1 neck injuries in frontal impacts--a parameter study combining field data and Madymo modeling

Two situations with an expected higher AIS 1 neck injury rate in frontal impact were compared to a reference situation using a Madymo human body model in three different sitting postures and four different crash pulses. The two situations were reduced occupant weight and occupant with initial forward arm resistance, respectively. Occupant neck motion phases were identified and corresponding possible evaluation criteria were evaluated within the phases. Typical neck kinematics was seen for the two different situations. Occupants of lower weight had a more extended neck in the initial protraction phase and also a generally more pronounced upper neck link angle. Occupants with initial arm resistance had generally greater lower neck link angle at the time when the upper neck link angle was straight. No evaluation criteria reflected the anticipated AIS 1 neck injury rate consistently. In the initial protraction phase, NICmin correlated to expected injury outcome in almost half of the cases. In the protraction-flexion shift phase, Nkm, Nij, upper neck shear force and neck tension force reflected anticipated severity outcome to some extent. In the flexion phase, upper and lower neck extension correlated to anticipated AIS 1 neck injury rate only to a minor extent. The different sitting postures were more influential than the different crash pulses, emphasizing the importance of not only considering the spectra of impact severity but also differences in sitting postures in safety system development and evaluation.     

Depletion of coastal predatory fish sub-stocks coincided with the largest sea urchin grazing event observed in the NE Atlantic

In this contribution, we propose fishery driven predator release as the cause for the largest grazing event ever observed in the NE Atlantic. Based on the evolving appreciation of limits to population connectivity, published and previously unpublished data, we discuss whether overfishing caused a grazer bloom of the sea urchin (Strongylocentrotus droebachiensis) resulting in overgrazing of more than 2000 km² kelp (Laminaria hyperborea) forest along Norwegian and Russian coasts during the 1970 s. We show that coastal fisheries likely depleted predatory coastal fish stocks through modernization of fishing methods and fleet. These fish were important predators on urchins and the reduction coincided with the urchin bloom. From this circumstantial evidence, we hypothesize that coastal predatory fish were important in regulating sea urchins, and that a local population dynamics perspective is necessary in management of coastal ecosystems.