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.

Organotin compounds in surface sediments from seaports on the Gulf of Gdansk (southern Baltic coast).

Sediment samples were collected in two Polish ports of international significance--the Port of Gdansk and the Port of Gdynia (Gulf of Gdansk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdansk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.

Plastic-derived contaminants in sediments from the coastal zone of the southern Baltic Sea.

Plastics may leach out harmful chemicals, such as plastic additives and monomers, to the environment. This study focused on three intrinsic plastic-derived contaminants, viz. bis(2-ethylhexyl) phthalate (DEHP), bisphenol A (BPA), and styrene, based on surface (0-5 cm) sediment samples taken from transition areas located in the human-impacted coastal zone of the southern Baltic Sea. The concentrations of DEHP in the sediments from the Gulf of Gdansk and the Szczecin Lagoon ranged from 38 to 228 ng/g d.w. and from 494 to 807 ng/g d.w., respectively. The levels of sedimentary BPA varied from <1 to 32 ng/g d.w., whereas styrene was not detected in any of the samples studied. Compared to worldwide data, the levels of plastic-derived contaminants in the sediments from the Gulf of Gdansk and the Szczecin Lagoon were generally not high. However, according to sediment quality guidelines, some adverse environmental effects are probable.

Butyltins in sediments from the Southern Baltic coastal zone: Is it still a matter of concern, 10 years after implementation of the total ban?

The study was done to assess butyltin contamination in sediments of the Southern Baltic coastal zone, ten years after implementation of the total ban on harmful organotin use in antifouling paints. Sediment samples were collected from two seaports of international significance: the Port of Gdansk and the Port of Gdynia, as well as from the Szczecin Lagoon which plays a significant role as a shipping route connecting the Port of Szczecin with the Port of Swinoujscie. Total concentrations of butyltins in the sediment samples ranged between 5.7 and 3321 ng Sn g-1 d.w. Eighty percent of the samples were found as highly and grossly contaminated with tributyltin. The results were compared with those recorded ten years ago. Despite the improvement, the butyltin contamination still gives rise to concern in the study area. According to the HELCOM recommendation, all samples exceeded the Good Environmental Status boundary for tributyltin in sediments.

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 Gdansk (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.

Chloropigments a in the Gulf of Gdansk (Baltic Sea) as markers of the state of this environment.

The Gulf of Gdansk receives the waters of the Wisla (Vistula), the largest Polish river and the second largest river flowing into the Baltic Sea. Chloropigments a (chlorophyll a and its derivatives) were determined in water and sediments from the Gulf. Samples were collected during cruises of R.V. 'Oceania' at 19 stations located at different water depths and distances from the shore, in May (2003) and October (2004), i.e., at the beginning and at the end of the growing season, respectively. Seawater was also sampled on the beach at Sopot in June, July and August 2004, i.e., during the height of the growing season. All water samples were collected with a bathometer and passed through Whatman GF/F filters. Recent sediments (0-10 cm) were collected with a core sampler and divided into sub-samples (0-1, 1-5 and 5-10 cm). The pigments were determined using HPLC-DAD. The results were first correlated with a set of parameters measured in situ during sample collection (salinity, temperature, oxygen content of seawater) and determined in the same material (organic carbon content, granulometry), then worked up statistically. Although this investigation shows that particular chloropigments a in recent sediments are indicative of the prevailing environmental conditions in the study area and the trends in their variations, they should be treated as a relative and not an absolute measure, since this is the first such study based on a large and coherent set containing both chloropigment a and environmental data. In addition, a chlorophyll a budget is estimated for the Gulf of Gdansk on the basis of the literature and the authors' own data. Only c. 10% of the chlorophyll a produced annually in the Gulf of Gdansk is transferred to sediments in the form of chloropigments a; 2.8% is in the form of undecomposed chlorophyll a and 7.2% in the form of chlorophyll a derivatives. About 90% of chlorophyll a is decomposed to colourless products.

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.

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.

Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS).

The laboratory characterization of a field-operable surface-enhanced Raman scattering sensor (SERS optode) is presented for the detection of aromatic hydrocarbons in seawater. The sensor has been developed for deployment with a robust underwater spectrograph. To meet the demands of the harsh seawater application, sol-gel derived SERS substrates were used. The calibration curves of six PAHs were determined to be of Langmuir adsorption isotherm type with limits of detection ranging from the microg l(-1) to ng l(-1) level. The experimentally determined adsorption constants varied strongly with the molecular weight of the analytes and correlated with their solubility. A mixture of five PAHs dissolved in seawater was investigated to demonstrate the utility of this method for screening. Emphasis was put on the interference from suspended particulate matter (SPM). The Raman measurement with backscattering configuration was shown to be immune against turbidities up to 1000 NTU. The physico-chemical interference arising from adsorption by the sediment was measured on-line by adding sediment to a PAH-spiked solution. According to the calibration curve, the PAH concentration decrease corresponded to more than 98% of the analyte being scavenged by the sediment.

Organotin compounds in surface sediments of the Southern Baltic coastal zone: a study on the main factors for their accumulation and degradation.

Sediment samples were collected in the Gulf of Gdansk, and the Vistula and Szczecin Lagoons-all located in the coastal zone of the Southern Baltic Sea-just after the total ban on using harmful organotins in antifouling paints on ships came into force, to assess their butyltin and phenyltin contamination extent. Altogether, 26 sampling stations were chosen to account for different potential exposure to organotin pollution and environmental conditions: from shallow and well-oxygenated waters, shipping routes and river mouths, to deep and anoxic sites. Additionally, the organic carbon content, pigment content, and grain size of all the sediment samples were determined, and some parameters of the near-bottom water (oxygen content, salinity, temperature) were measured as well. Total concentrations of butyltin compounds ranged between 2 and 182 ng Sn g(-1) d.w., whereas phenyltins were below the detection limit. Sediments from the Gulf of Gdansk and Vistula Lagoon were found moderately contaminated with tributyltin, whereas those from the Szczecin Lagoon were ranked as highly contaminated. Butyltin degradation indices prove a recent tributyltin input into the sediments adjacent to sites used for dumping for dredged harbor materials and for anchorage in the Gulf of Gdansk (where two big international ports are located), and into those collected in the Szczecin Lagoon. Essential factors affecting the degradation and distribution of organotins, based on significant correlations between butyltins and environmental variables, were found in the study area.

The use of surface-enhanced Raman scattering (SERS) for detection of PAHs in the Gulf of Gdansk (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 Gdansk (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 Gdansk 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 Gdansk 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 Gdansk 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.