Ludwik Lubecki

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.

Indices of PAH Origin—A Case Study of the Gulf of Gdańsk (SE Baltic) Sediments

The aim of this work is to present a way of developing indices for assessing the dominant origin of polycyclic aromatic hydrocarbons (PAHs) on the basis of a case study in the Gulf of Gdańsk (SE Baltic). The indices were based on selected concentration ratios of both parent and alkylated PAHs found in reference matrices that are potential anthropogenic sources of PAH pollution for this area, i.e., airborne particulate matter (PM10) from the Gdańsk conurbation, soot derived from wood and diesel oil combustion, and a variety of petrogenic products. Verification of the suitability of the PAH ratios for source apportionment showed that the following indices are potentially the most useful for distinguishing PAHs of pyrogenic and petrogenic origin: [Σ3-+Σ4-ring-PAHs]/[Σ5-+Σ6-ring-PAHs], ΣmMP/Phen, 4,5-MP/ΣmMP, 1,7-dMP/[1,7-+2,6-dMP]. It was found that PAHs deposited in recent sediments in the Gulf of Gdańsk originate mainly from pyrogenic sources, while perylene is also derived from diagenetic processes.

Determination of 4-nonylphenols in sediments from a eutrophic marine area

The aim of this work was to develop a simple and efficient analytical method for the determination of 4-nonylphenols (4-NPs) in marine sediments. Nonylphenols are a group of xenobiotics of great environmental concern owing to their endocrine-disrupting properties; they are recognised as priority pollutants by the Water Framework Directive. The analytical procedure involves ultrasonic extraction followed by two-step solid phase extraction clean-up and gas chromatography–mass spectrometry analysis, without a derivatisation step. The method was validated and demonstrated to be suitable for marine sediments rich in organic matter from a eutrophic, contaminated area; 4-NP recovery rates were above 90%. This method was applied to the analysis of 4-NPs in recent sediments from the Gulf of Gdańsk (Southern Baltic Sea). Sediments from this area are moderately contaminated with 4-NPs (0–1 cm layer: 1–42 ng/g d.w.; 1–5 cm layer: 2–61 ng/g d.w.).

Vertical profiles of sedimentary polycyclic aromatic hydrocarbons and black carbon in the Gulf of Gdańsk (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 Gdańsk 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 Gdańsk, 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 Gdańsk (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 Gdańsk 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 Gdańsk were not as obvious. The historical PAH trends in the Gulf of Gdańsk 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 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.