Grażyna Kowalewska

Polychlorinated biphenyls (PCBs) in sediments of the southern Baltic Sea — trends and fate

Polychlorinated biphenyls (PCBs) have been determined in recent [0-1(2), 1(2)-5 and 5-10 cm deep layers] sediments from different sites of the southern Baltic Sea, including the Szczecin Lagoon, collected from May 1996 to October 1999, i.e. before and after the great flood in Poland of July/August 1997. The PCB distribution has been correlated with location and hydrological conditions as well as with organic carbon, algal pigments and their derivatives in the sediments. The sum of PCB (seven congeners) was equal to approximately 1-149 ng/g dry wt., on average this was rather low (up to 40 ng/g). There was a decreasing trend in PCBs concentrations in the bottom sediments of the southern Baltic in 1996 but considerable amounts were still accumulated there. The flood of 1997 caused a distinct increase of PCB concentration level in the sediments, which again showed a decreasing trend in the next few years. This illustrates that at present the main source of PCBs for the southern Baltic are not a direct consequence of human activity, but from floods and heavy rains washing these compounds from land to the sea. Algae and algal detritus play an important role in the transport and distribution of PCBs in the southern Baltic. High correlation of PCBs with chlorophyll a derivatives--products of zooplankton grazing--indicates that PCBs are ingested by zooplankton with phytoplankton and then exuded with fecal pellets. PCBs bound to algal detritus or to fecal pellets in the water column are transferred to sediments, there they may be trapped either in a bonded and unchanged form or resuspended, remobilized and/or dechlorinated, depending on their properties and environmental conditions.

Transfer of organic contaminants to the Baltic in the Odra Estuary

This paper describes the transfer of organic contaminants to the sea, using PAHs (12 compounds) and PCBs (11 congeners) as examples, through a eutrophicated coastal lagoon (Szczecin Lagoon, on the Polish-German border). The transfer of contaminants study was based on their concentration in recent sediments (0-10 cm), in relation to different environmental conditions such as temperature, salinity, turbidity, oxygen and nutrients in water, hydrological conditions, organic carbon and biomarkers (pigments and their derivatives) in sediments. Results include the data obtained between 1994 and 2000, also those on before and afterwards the great flood in July 1997, at different stations in the Lagoon and the adjacent Pomeranian Bay. The results indicated that the eutrophic estuary of the shape of lagoon acts as an effective trap for the hydrophobic organic pollutants. The abundance and taxonomy of plankton as well as detritus derived from it play an important role in bonding the studied compounds. The salinity gradient in the lagoon has a significant influence upon deposition of the pollutants from the water column to the sediments and the residence time of the compounds there depends strongly on oxic-anoxic status of the sediments and the strength of interaction with sediments resulting from polarity, the type and stability of associates formed, as well as on hydrological conditions. We conclude that eutrophication in this area prevents pollution of the sea to some extent.

Nutrient content in macrophyta collected from southern Baltic Sea beaches in relation to eutrophication and biogas production

One of the signs of eutrophication is the excessive growth of opportunistic macroalgae, a worldwide phenomenon also observed in the Baltic Sea. Mats of macroalgae may drift long distances and accumulate at the seashore, considerably decreasing the recreational value of beaches. The matter accumulating at the shore is treated usually as waste. However, it could be used, for example, as a resource for biogas production. The aim of this work was to verify the hypothesis that collecting of macrophyta accumulating on the beach and potential usage of this material for biogas production will decrease nutrient reserves in the sea to counteract eutrophication and the increase in greenhouse effects. Samples of macrophyta were collected in 2011 and 2012 and analysed for their C, N, and P contents, and degree of degradation (% Chl-a in the sum of chloropigments-a); the results were analysed statistically. The nutrient content was studied in macrophyta accumulating on the beach (Sopot, Gulf of Gdańsk, Poland) and for comparison, macrophyta collected from their habitats in less nutrient polluted area (off the Skåre coast, Trelleborg, Sweden). The nutrient content (N, P) in macrophyta depends primarily on their morphology and only secondarily on environmental nutrient pollution. Collecting the macrophyta biomass accumulating on beaches will not significantly change the eutrophication of the Baltic as a whole; any improvements in this respect are likely to be on a local scale only. Collecting macrophyta removes more nitrogen than phosphorous, so this would decrease the N/P ratio in seawater. This macrophyta biomass is a substantial reserve of renewable energy, which could be utilized with the appropriate technology for biomass collection/preservation and biofuel production as an additive to other carbon-rich biomasses. And the biofuel production should be evaluated not only from the standpoint of economic efficiency but also from the environmental point of view.

The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdańsk (Baltic Sea)

A field operable surface enhanced Raman scattering (SERS) sensor system was applied for the first time under real conditions for the detection of polycyclic aromatic hydrocarbons (PAHs) as markers for petroleum hydrocarbons in the Gulf of Gdańsk (Baltic Sea). At six stations, seawater samples were taken, and the sensor system was applied in situ simultaneously. These measurements were compared to the results of conventional GC/MS laboratory analysis of the PAH concentrations in the seawater samples. For a PAH concentration above 150 ng(12PAH)l(-1), there was agreement between the SERS sensor and the GC/MS determinations. A standard addition experiment yielded a PAH concentration of 900 ng l(-1) at the Gdańsk Harbor, which was of the same order as the GC/MS determinations of 12PAHs (200 ng(12PAH)l(-1)). The high SERS detection limit for seawater samples is explained by the competition for PAHs between the sensor membrane and particulate matter surfaces. Thus, the SERS sensor can be applied, e.g., as a non-quantitative alarm sensor for relatively high PAH concentrations in heavily polluted waters. The spectral unmixing procedure applied for Gdańsk Harbor water confirmed the presence of phenanthrene at the highest concentration ([Phe]=140 ngl(-1)) and of Chr (2.7 ng l(-1)), but it did not detect the other PAHs present in the Gdańsk Harbor water, as determined by GC/MS. When compared to the past literature and databases, the SERS spectra indicated the presence of a mixture of molecules consisting of carotenoids, n-alkanes, amines or fatty acids, and benzimidazoles at the coastal station ZN2. The spectra in the offshore direction indicated carboxylic acids. Interpretation of the farthest offshore in situ SERS measurements is difficult, principally due to the limited availability of reference spectra. The detection of the lower PAH concentrations commonly found in Baltic coastal water needs further research and development to obtain better sensitivity of the SERS sensor. However, the high analytical specificity of the SERS sensor also allows the detection of other chemical species that require the development of a SERS/Raman library for specific in situ spectral interpretation.

Comparison of Extraction and HPLC Methods for Marine Sedimentary Chloropigment Determinations

Abstract This study compared different extraction and high performance liquid chromatography (HPLC) combinations for the analysis of chloropigments in sediments and microalgae (phytoplankton). A significant literature review is also included. Extractants in the present study included 100% acetone, tetrahydrofuran, and an aqueous mixture of methanol, acetone, and dimethylformamide. HPLC methods involved gradient elution methods with or without ion pairing reagents over C18 silica based columns. Though slight differences were found, most notably with the extraction of steryl chlorin esters, this intercomparison reveals that both extraction and HPLC protocols investigated, in any combination, perform well for the analysis of chlorophylls and their derivatives in sediment and phytoplankton samples.

Steryl chlorin esters in sediments of the southern Baltic Sea

Sediments of the southern Baltic Sea were analysed for content of steryl chlorin esters, the chlorin compounds discovered recently in the marine environment. The chlorin esters occur in the Baltic sediments in substantial amounts and form a considerable fraction of the total chlorin content. Among the physicochemical parameters studied the highest correlation with the steryl chlorins showed organic carbon content in sediments and the content of fraction of sediments smaller than 10 μm. A significant correlation was observed between the steryl chlorins content and other chlorins as chlorophylla, phaeophytina, pyrophaeophytina as well as with β-carotene, the distinctly less significant correlation was with phaeophorbidea. This indicates an other way of formation of the steryl chlorins from algae than zooplankton grazing.

Organotins in fish muscle and liver from the Polish coast of the Baltic Sea: Is the total ban successful?

Muscle and liver tissues of nine fish species were analyzed to assess butyltin and phenyltin contamination. The samples were collected from three basins located in the Southern Baltic Sea coastal zone that each represent different potential for organotin pollution. Maximum total concentrations of butyltin compounds (BTs) in the fish muscles and livers were 715 and 1132ng Sn g(-1) d.w., respectively, whereas triphenyltin (TPhT) was not detected. In the muscle samples, the predominant compound in the sum of butyltins was tributyltin (TBT), while in the liver samples, tributyltin degradation products were found in the majority. The results demonstrate that 6-7years after the implementation of the total ban on harmful organotin use in antifouling paints, butyltins remain present in fishes from the Polish coast of the Baltic Sea. According to the HELCOM recommendation, eight samples exceeded the good environmental status boundary for tributyltin in seafood.

Anthropogenic impact on marine ecosystem health: A comparative multi-proxy investigation of recent sediments in coastal waters

Hazardous substances entering the sea, and ultimately deposited in bottom sediments, pose a growing threat to marine ecosystems. The present study characterized two coastal areas exposed to significant anthropogenic impact - Gulf of Gdańsk (Poland), and Oslofjord/Drammensfjord (Norway) - by conducting a multi-proxy investigation of recent sediments, and comparing the results in light of different available thresholds for selected contaminants. Sediment samples were analyzed for benzo(a)pyrene (B(a)P) and other polycyclic aromatic hydrocarbons (PAHs), nonylphenols (NPs), organotin compounds (OTs), toxic metals (Cd, Hg, Pb), as well as mutagenic, genotoxic and endocrine-disrupting activities (in CALUX bioassays). In general, a declining trend in the deposition of contaminants was observed. Sediments from both basins were not highly contaminated with PAHs, NPs and metals, while OT levels may still give rise to concern in the Norwegian fjords. The results suggest that the contamination of sediments depends also on water/sediment conditions in a given region.

Specific Chemical and Genetic Markers Revealed a Thousands-Year Presence of Toxic Nodularia spumigena in the Baltic Sea

In the Baltic Sea, diazotrophic cyanobacteria have been present for thousands of years, over the whole brackish water phase of the ecosystem. However, our knowledge about the species composition of the cyanobacterial community is limited to the last several decades. In the current study, the presence of species-specific chemical and genetic markers in deep sediments were analyzed to increase the existing knowledge on the history of toxic Nodularia spumigena blooms in the Baltic Sea. As chemical markers, three cyclic nonribosomal peptides were applied: the hepatotoxic nodularin, which in the sea was detected solely in N. spumigena, and two anabaenopeptins (AP827 and AP883a) characteristic of two different chemotypes of this species. From the same sediment samples, DNA was isolated and the gene involved in biosynthesis of nodularin, as well as the phycocyanin intergenic spacer region (PC-IGS), were amplified. The results of chemical and genetic analyses proved for the first time the thousands-year presence of toxic N. spumigena in the Baltic Sea. They also indicated that through all this time, the same two sub-populations of the species co-existed.