Application of various molecular markers for investigating petrogenic inputs in coastal systems strongly impacted by anthropogenic stressors.

In this study, multiple molecular markers [polycyclic aromatic hydrocarbons (PAHs), linear and branched alkanes, unresolved complex mixture (UCM), hopanes, and steranes] were applied to explore petroleum-related inputs in complex coastal systems influenced by various human-induced pressures. To investigate anthropogenic impacts related to petrogenic emissions, we analysed surface sediments from coastal areas of southern Baltic, including harbour/shipyard channels, offshore dumping sites, shipping routes, and major sinks for particulate matter discharged by large rivers. This study indicates a large spatial variability in the contamination degree of examined sites by petroleum-derived chemicals. Hopanes and steranes along with UCM appeared to have the highest potential to identify petroleum sources in studied locations, whereas investigations based on alkanes and PAHs seemed to be considerably affected by inputs of modern biogenic and combustion-derived materials, respectively. However, the combined use of all these markers provides deeper insight into the complexity of sedimentary organic matter in human-impacted environments.

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.

Vertical profiles of sedimentary polycyclic aromatic hydrocarbons and black carbon in the Gulf of Gdansk (Poland) and Oslofjord/Drammensfjord (Norway), and their relation to regional energy transitions.

The analysis of undisturbed sediment cores is a powerful tool for understanding spatial and temporal impacts of anthropogenic emissions from the energy and transport sectors at a regional scale. The spatial and vertical distribution of polycyclic aromatic hydrocarbons (PAHs) and black carbon (BC) were determined in 12 cores of recent (up to 20cm long) sediments from the Gulf of Gdansk in Poland, and Oslofjord/Drammensfjord in Norway. The Σ12PAHs levels in individual sediment layers varied from 250 to 4500ng/g d.w. in the Gulf of Gdansk, and from 210 to 4580ng/g d.w. in the Norwegian fjords. Analysis of PAH ratios indicates that PAHs in both studied areas originated mainly from pyrogenic sources. The BC concentrations in sediments were up to 0.9% and were generally higher in the Gulf of Gdansk (mean - 0.39%) than in Oslofjord/Drammensfjord (mean - 0.19%). The deposition history of anthropogenic emissions over the last 100years was reconstructed based on the analysis of dated and well-laminated sediment cores from two stations from the Gulf of Gdansk and two stations from the Norwegian fjords. The evolution in energy structure was especially evident in the Oslofjord, where transition from fossil fuel combustion to hydropower after 1960 coincided with a sharp decrease in sedimentary PAHs. Despite significant changes in the economic development in Poland, temporal patterns in PAH concentrations/profiles in the Gulf of Gdansk were not as obvious. The historical PAH trends in the Gulf of Gdansk may be related to the overwhelming PAH inputs from domestic combustion of solid fuels (coal, wood) for heating purposes. The implementation of legislation and other activities addressed to restrict the use of solid fuels in residential heating should reduce PAH emissions.

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.

Endocrine disruptors in blue mussels and sediments from the Gulf of Gdansk (Southern Baltic).

Samples of blue mussel (Mytilus trossulus) and sediment were collected in the Gulf of Gdansk (Southern Baltic Sea) to assess the extent of their contamination with two groups of endocrine disruptors: 4-nonylphenols and organotins (butyl- and phenyltins). Five sampling stations were chosen along the coastline of the Tricity Agglomeration (Gdansk, Sopot, Gdynia) in 2008, 2012, and 2013. No evident differences between the three campaigns were found in either the mussel or the sediment samples. The mussels were moderately contaminated with 4-nonylphenols (30-111 ng g(-1) d.w.), whereas the levels of these compounds in the sediment samples were very low (0.8-2.7 ng g(-1) d.w.). Total concentrations of butyltin compounds in the mussels and sediments ranged between 41 and 164 ng Sn g(-1) d.w., and from below the limit of detection to 22 ng Sn g(-1) d.w., respectively, whereas phenyltins were not detected in any of the samples. Butyltin degradation indices indicate an old tributyltin input into the coastal environment, which is characterized by intense maritime activity. The results obtained from this work demonstrate that 5 years after the total ban on using organotin-based antifouling paints was imposed, butyltins are still present in mussels and sediments of the Gulf of Gdansk.

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.