Temporal trends of PCDD/Fs in Baltic Sea sediment cores covering the 20th century.

The pollution trend of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea region was studied based on depth profiles of PCDD/Fs in sediment cores collected from six offshore areas, eight coastal sites impacted by industrial/urban emissions, and one coastal reference site. A general trend was observed for the offshore and coastal reference sites with substantial increase in PCDD/F concentrations in the mid-late 1970s and peak levels during 1985-2002. The overall peak year for PCDD/Fs in Baltic Sea offshore areas was estimated (using spline-fit modeling) to 1994 ± 5 years, and a half-life in sediments was estimated at 29 ± 11 years. For the industrial/urban impacted coastal sites, the temporal trend was more variable with peak years occurring 1-2 decades earlier compared to offshore areas. The substantial reductions from peak levels (38 ± 11% and 81 ± 12% in offshore and coastal areas, respectively) reflect domestic and international actions taken for reduction of the release of PCDD/Fs to the environment. The modeled overall half-life and reductions of PCDD/Fs in offshore Baltic Sea sediment correspond well to both PCDD/F trends in European lakes without any known direct PCDD/F sources (half-lives 30 and 32 years), and previously modeled reduction in atmospheric deposition of PCDD/Fs to the Baltic Sea since 1990. These observations support previous findings of a common diffuse source, such as long-range air transport of atmospheric emissions, as the prime source of PCDD/Fs to the Baltic Sea region. The half-life of PCDD/Fs in Baltic Sea offshore sediments was estimated to be approximately 2 and 4-6 times longer than in semirural and urban European air, respectively. This study highlights the need for further international actions to reduce the levels of PCDD/Fs in Baltic Sea air specifically and in European air in general.

Comparing spatial and temporal changes in metal trends (Cr, Ni, Pb and Zn) on the Portuguese shelf since the 1970s.

Comparison between an archive dataset, collected during the 1970s (1974-1977), and samples taken during the PALEO1 cruise (2002) enabled evaluation of large-scale and long-term spatiotemporal changes in Al, Cr, Ni, Pb and Zn contents in bulk surface sediments in four areas of the Portuguese shelf. The so-called gradient method (GM) with normalisation to Al, a proxy for terrigenous clay content, was applied. The studied areas are distributed from north to south along the western margin, with the northernmost located off shore the Ave and Douro rivers, a central one located off shore the Lis River and a southern one located off shore the Mira River. One-way ANOVA and Kruskal-Wallis tests were used to identify differences among study areas and periods of sample collection. A comparison of metal contents in 2002 samples with the Portuguese classification scheme regulation for deposition of dredged materials in coastal areas indicates good environmental quality in terms of Cr, Ni, Pb and Zn levels. Nevertheless, the GM results suggest an increase in metal loadings relative to Al from the 1970s to the 2002 samples (except for Pb). The Algarve area on the southern shelf is characterised by having high number of sites with metal level on class 2. These high values have traditionally been explained by a substantial supply of natural metals from the Guadiana, Tinto and Odiel rivers that drain areas Iberian Pyrite Belt formations. This supply has probably been magnified by present and past mining activities. For quality evaluation of marine sediments, especially when using total metal contents, this study shows the importance of considering all possible sources of metal loading. The natural grain size and composition variability have also a crucial influence on the metal content, and the combined evaluation allows a more holistic perspective.

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea.

BACKGROUND, AIM, AND SCOPE: The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. MATERIALS AND METHODS: Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. RESULTS: Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. DISCUSSION: The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. CONCLUSIONS: The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. RECOMMENDATIONS AND PERSPECTIVES: In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended.

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.

Sulfur and iron accumulation in three marine-archaeological shipwrecks in the Baltic Sea: the Ghost, the Crown and the Sword.

Sulfur and iron concentrations in wood from three 17(th) century shipwrecks in the Baltic Sea, the Ghost wreck, the Crown and the Sword, were obtained by X-ray fluorescence (XRF) scanning. In near anaerobic environments symbiotic microorganisms degrade waterlogged wood, reduce sulfate and promote accumulation of low-valent sulfur compounds, as previously found for the famous wrecks of the Vasa and Mary Rose. Sulfur K-edge X-ray absorption near-edge structure (XANES) analyses of Ghost wreck wood show that organic thiols and disulfides dominate, together with elemental sulfur probably generated by sulfur-oxidizing Beggiatoa bacteria. Iron sulfides were not detected, consistent with the relatively low iron concentration in the wood. In a museum climate with high atmospheric humidity oxidation processes, especially of iron sulfides formed in the presence of corroding iron, may induce post-conservation wood degradation. Subject to more general confirmation by further analyses no severe conservation concerns are expected for the Ghost wreck wood.

Congener fingerprints of tetra- through octa-chlorinated dibenzo-p-dioxins and dibenzofurans in Baltic surface sediments and their relations to potential sources.

Comprehensive congener fingerprints of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), including non-2,3,7,8-substituted congeners, in 142 surface sediment samples from the Baltic Sea were characterized by Principal Component Analysis (PCA). The pattern analysis revealed source specific indicators of chlorophenol use, high temperature processes, chlorine bleach/chloralkali production and a source signature suggested to originate from pulp/paper or related production. Congener patterns in sediments from offshore and pristine coastal areas showed strong resemblance to patterns of atmospheric deposition and flue gases, indicating that these sources have high impact in areas that are not affected by point sources. Prominent contributors to the patterns of hotspot areas along the Swedish coast included chlorophenol indicators and a source characterized by hexa-CDDs while the contribution of the traditional chlorine bleach pattern was weaker. This study demonstrates the importance of comprehensive PCDD/F congener analysis for identifying links to candidate sources.