Spatial distribution of phosphorus forms in sediments in the Gulf of Gdańsk (southern Baltic Sea)

The paper analyses the concentrations of total phosphorus and its forms in sediments from the Gulf of Gdańsk on the basis of studies conducted at 25 sampling sites in 2001–05. The phosphorus speciation analysis was performed by sequential extraction. The extensive spatial variability of P_tot concentrations and speciation was found to be dependent on the physicochemical properties of the sediments, the oxygen conditions in the water and sediments, and the depth of the water column above the sediment surface. In the coastal zone, the sedimentation of riverine suspended matter and the sorption and chemisorption processes exert a considerable influence on P speciation. Over 70% of variation of total phosphorus concentration in sediments in the Gulf of Gdańsk could be explained by changes of proportion of fine fraction of sediments (grain size <0.0625 mm). Maximum P_tot concentrations were recorded in clays and silts in the deep water, stratified part of the Gulf of Gdańsk. In the coastal zone, where sandy sediments are dominant, phosphorus concentrations were much lower; this was due to the considerable dynamics of the bottom water and intensive sea floor transport. P_tot concentrations in the Gulf of Gdańsk sediments ranged from 1.75 to 957.17 μmol g⁻¹ d.w. Of all the forms of phosphorus, the highest concentrations were found for organic phosphorus (Org-P). Of its inorganic forms, the highest concentrations were of phosphorus bound to clay minerals and aluminium oxides (NaOH-P), the lowest ones were of loosely bound phosphorus (NaCl-P). On the basis of determinations of total phosphorus concentrations in sediments of a given type and the available data on the seabed areas covered by particular sediment types in the Gulf of Gdańsk, the mass of total phosphorus in the surficial sediment layer (0–2 cm) was estimated at ca. 15.6×10³ tonnes.     

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.     

Monitoring of organic pollutants in coastal waters of the Gulf of Gdańsk, Southern Baltic

This paper presents an overview of changes in organic pollution of coastal waters of the Gulf of Gdańsk (Baltic Sea). Toxic pollutants including volatile organic compounds (VOC), volatile organohalogen compounds (VOX), chlorophenols, phenoxyacids, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were determined in seawater from the Gulf of Gdańsk coastal waters in the period 1996-2001. In the case of the Gulf of Gdańsk, non-conservative behaviour of VOC was observed due to random temporal and spatial of inputs along the Vistula estuary and to the dilution of VOC-enriched river water with seawater. The concentrations of VOX in seawater decreased throughout the period and the concentrations of VOX were in the range of few ng dm(-3) up to 250 ng dm(-3), similar to estuaries elsewhere. The average concentrations of chlorophenols and phenoxyacids were between 0.1 and 6.0 and 0.05 and 2.2 microg dm(-3), respectively. However, remarkably high concentrations of 2,4-dichlorophenol (6 microg dm(-3)) were obtained in samples collected from the Vistula River. Generally concentrations of PCBs did not exceed few ng dm(-3) with the exception of 1999, when all samples exhibited elevated concentrations of PCBs. In addition, higher concentrations of PCBs in the open sea compared to river waters suggested localised inputs. Due to the ability of most organic pollutants to bioaccumulate and biomagnify, especially the persistent organic pollutants, continued monitoring is of crucial importance for the health of marine life in the Gulf of Gdańsk.     

The relationship between the concentrations and distribution of organic pollutants and black carbon content in benthic sediments in the Gulf of Gdańsk, Baltic Sea

The influence of the sediment’s physico-chemical properties and black carbon content, on the distribution of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in benthic sediments of the Gulf of Gdansk (Baltic Sea) was determined. Sediments from port, marine dump site of dredged spoils, the Vistula river mouth, Gdansk Deep were selected.The concentrations of ∑PAHs (fluoranthene, pyrene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene) were 294-2200 ng/g d.w. and for ∑PCBs (28, 52, 101, 118, 138, 153, 180) were 2.4-11.3 ng/g d.w.The sediments content of loss on ignition was 1.13-16.15%, total organic carbon was 0.89-7.15%, black carbon was 0.20-1.15%. The highest correlation coefficient values (r = 0.76-0.92, p < 0.05) for a relationship between the concentrations of organic pollutants, and organic matter, organic and black carbon contents were obtained in harbor sediments with low content of organic matter (<5%) and high share of black carbon in total carbon (up to 40%).     

The sanitary state of Pomeranian Bay and Gulf of Gdańsk waters during the flood of 1997

Summary Due to the 1997 summer flood, the Pomeranian and Gdańsk Bays were polluted with a significant amount of bacteriologically contaminated Oder and Vistula rivers waters. The purpose of this study was to determine the sanitary state of both bays during the flood and directly after it, the range of direction of distribution of the bacteriological contamination brought in by Vistula and Oder waters. On the basis of examination results, the sanitary state of the bays waters was found to be worse, particularly with regard to indicators: total bacterial number (at 20 °C and 37 °C) and Most Probable Number (MPN) of coliform and faecal coliform bacteria. Bacteria of the Pseudomonas group(Pseudomonas aeruginosa, Pseudomonas fluorescens), Enterobacteriaceae group (m.in.Proteus vulgaris), as well as enterococci(Streptoccus) and staphylococci(Staphylococcus) were found in water samples from Pomeranian and Gdańsk Bays. In the Pomeranian Bay the waters spread to the west (due to weather conditions), whereas in Gdańsk Bay they remained mainly in the coastal zone and then moved to the east. An improvement in the sanitary state of both bay waters was observed at the end of August. Zusammenfassung W?hrend des Sommer-Hochwassers 1997 wurden die Gew?sser der Pommerschen und der Danziger Bucht mit kontaminiertem Wasser aus den Flüssen Oder und Weichsel verunreinigt. Ziel dieser Arbeit ist es, den Grad der bakteriellen Verunreinigungen durch einstr?mendes Flu?wasser aus Oder und Weichsel in die Pommersche und die Danziger Bucht w?hrend des Hochwassers und direkt danach zu bestimmen. Auf der Basis von Messungen wurde eine Vermehrung von Colibakterien im Wasser beider Buchten unter Berücksichtigung folgender Indikatoren festgestellt: 1. Gesamtzahl an Bakterien (Wassertemperatur 20 °C and 37 °C) und 2. vermuteter Anteil von gesamtcoliformen und f?kalcoliformen Bakterien. Die Wasserproben aus der Danziger und der Pommerschen Bucht enthielten sowohl F?ulnisbakterien(Pseudomonas aeruginosa, Pseudomonas fluorescens) als auch Bakterien aus der Gruppe der Enterobacteriaceae(Proteus vulgaris), Staphylokokken(Staphylococcus) und F?kalstreptokokken(Streptococcus). Infolge Wetterver?nderung verlagerte sich das kontaminierte Wasser aus der Pommerschen Bucht nach Westen. In der Danziger Bucht hingegen blieb das kontaminierte Wasser zun?chst im Küstenbereich und verlagerte sich dann ostw?rts. Ende August wurde eine Verbesserung der Wasserqualit?t in beiden Buchten ermittelt.     

Measurements of biomarker levels in flounder (Platichthys flesus) and blue mussel (Mytilus trossulus) from the Gulf of Gdańsk (southern Baltic)

In the framework of the EU funded BEEP project a set of biomarkers, gross morphometric indices and tissue concentrations of selected organic pollutants were measured in flounder (Platichthys flesus) and mussels (Mytilus trossulus) collected twice a year (April and October) from three sites in the inner Gulf of Gdańsk between autumn 2001 and spring 2003. In flounder, seasonal differences in most biomarkers were observed, but no correlations with tissue pollutant levels could be found. In mussels, highly variable levels in biomarker responses were seen, but no clear seasonal or spatial trends, directly related to tissue concentrations, could be established. The observed biomarkers distribution the study sites are probably mostly caused by interannual, seasonal and individual variability and, in case of flounder, possibly by exchange of stocks between the sampling sites.     

Seasonal variability of the organic matter in a sedimentary coastal environment: sources,degradation and accumulation (continental shelf of the Gulf of Lions—northwestern Mediterranean Sea)

The temporal variations of the superficial (0–1 cm) sedimentary organic matter were studied at a depth of 26 m on the continental shelf of the Gulf of Lions (northwestern Mediterranean). The samples were analyzed for total organic carbon, coarse organic carbon (>40 μm), hydrolyzable organic carbon, nitrogen, total amino acids, total and individual sugars (HPLC), lignin-derived compounds (HPLC) and kerogens (acid-soluble, humic substances and humin). Seasonal variations of the organic compounds are related to the sedimentological, hydrodynamical and physico-chemical environmental conditions.The mean annual values of the different organic compounds analyzed show the low quantities and their evolved character at the sediment-water interface: 0.5% total org C (TOC) (d.w.), 0.049% N (d.w.), $\text{C}\text{N}$: 11.2, coarse org C (COQ: 62% of TOC, hydrolyzable org C: 45% TOC. The labile compounds represent a low percentage of the total organic matter (TOM), amino-acids: 12% of TOM and sugars: 5% of TOM. The relative proportions of soluble (humic) and insoluble kerogens (humin), respectively 6% and 94% of TOC are typical of a highly evolved organic matter. The large contribution of plant remains confirmed by the high proportion of COC, corresponds to a low proportion of humic substances and a high degree of condensation ($\text{H}\text{C}\text{= 1.3}$). The infrared spectroscopy determination of the functional groups of the humic substances permits us to confirm both autochtonous (marine) and allochtonous (terrestrial) sources of organic matter in the Têt prodeltaïc accumulation area. Numerous functional groups identified reveal the fresh quality of the organic inputs at the sediment-water interface. Aliphaticity is well marked and nitrogenous compounds (1 and 2 amines) correspond to autochtonous production (in spring: phyto- and zoo-planktonic blooms in the euphotic zone; in summer: primary production under the thermocline and phytobenthic blooms). Sugars are well represented, but from two origins: phytoplanktonic, and issue from terrestrial high plants (ligno-cellulosic complexes). The aromatic functional groups are well identified (aromatic ether, phenol) as are the markers of a large contribution of terrestrial organic matter.The active hydrodynamical (resuspension) and biological, (consumption, bioturbation) events participate in the frequent reworking of the superficial deposits (muddy-silts) and, consequently, the active degradation (oxidization) of the organic matter. The more labile organic matter is rapidly consumed by the intense biological benthic activity. The organic C content is low (0.5% d.w.) except during the autumnal input (2.5% d.w.). This input (8 cm thick) disappears one month later, because of the resuspension induced by littoral currents. This same phenomenon induces during all the year the reworking of the first centimeter of the deposit. In terms of budget of the carbon cycle in the coastal area, this active hydrodynamical environment shows the supremacy of the carbon degradation over its burial.     

Dreissena polymorpha (Bivalvia: Dreissenidae) in the Neva Estuary (eastern Gulf of Finland, Baltic Sea): is it a biofilter or source for pollution?

The zebra mussel Dreissena polymorpha, a ponto-caspian byssate bivalve, forms permanent dense populations along the shoreline in the northern part of the inner Neva Estuary. Its total biomass along a 17 km transect reached 4980 tons (mean 1060 g m(-2)) in 2000 and 6510 tons (mean 1385 g m(-2)) in 2001. Being persistent and abundant, the zebra mussel populations played an important role in benthic-pelagic coupling in inner Neva River Estuary. The D. polymorpha population released up to 514 kg day(-1) of dissolved inorganic phosphorus and was, therefore, a major source of bioavailable nutrients in the area. Mussel beds were also efficient biofilters and precipitate 15,020 kg day(-1) of particulate organic matter during the warm season. About 50% of precipitated matter had a relatively long retention time, being utilized within zebra mussel populations, while the rest was deposited as faeces and pseudofaeces and served as a source for organic pollution to the eastern Gulf of Finland.     

δ15N variation in Ulva lactuca as a proxy for anthropogenic nitrogen inputs in coastal areas of Gulf of Gaeta (Mediterranean Sea)

We tested the capacity of Ulva lactuca to mark N sources across large marine areas by measuring variation in its δ¹⁵N at several sites in the Gulf of Gaeta. Comparisons were made with the macroalga Cystoseira amentacea. Variation of δ¹⁵N values was assessed also in the coastal waters off the Circeo Natural Park, where U. lactuca and C. amentacea were harvested, as these waters are barely influenced by human activities and were used as reference site. A small fragment from each frond was preserved before deployment in order to characterize the initial isotopic values. After 48 h of submersion, U. lactuca was more responsive than C. amentacea to environmental variation and δ¹⁵N enrichment in the Gulf of Gaeta was observed. The spatial distribution of δ¹⁵N enrichment indicated that different macro-areas in the Gulf were affected by N inputs from different origins. Comparison of the δ¹⁵N values of fragments taken from the same transplanted frond avoided bias arising from natural isotopic variability.     

Abnormal features of Macoma balthica (Bivalvia) in the Baltic Sea: alerting symptoms of environmental adversity?

Recent studies of the Baltic clam Macoma balthica (L.) from the southern Baltic (the Gulf of Gdansk) have revealed striking morphological, histological and cytogenetic features. Strong deformation of the shell, including elongation of the posterior end and the appearance of an easily visible flexure in this part, has been recorded. The population contribution of the deformed blunt shelled ("irregular") clams ranged from 0% to 65% and tended to increase with depth. The morphologically "irregular" clams had higher accumulated tissue concentrations of trace metals (As, Ag, Cd, Pb, Cu and Zn), indicating a different metal handling ability. Adverse conditions in deeper water regions of the Gulf (e.g. hypoxia, hydrogen sulphide, elevated bioavailability of contaminants) have been suggested as inducers of the phenotypical changes (morphological deformation) in part of the population and, in parallel, of the specific physiological adaptations that result in higher metal accumulation in the "irregular" clams. Cytogenetic and histological analyses showed the presence of tumours in gill cells and digestive system of the affected clams, the prevalence of disseminated neoplasia ranging from 0% to 94% depending on the site. The disease was manifested by a modified karyotype (i.e. an abnormal number and morphology of chromosomes), a higher activity of nucleolar organizer regions (AgNORs), and tissue lesions (enlarged cells, actively proliferative with pleomorphic nuclei). Bottom sediments showed acute toxicity and have been proposed as a source of an initialising carcinogenic factor. However, none of the ecotoxicological studies provided was successful in the clear demonstration of a single (or multifactorial) agent that can account for the disseminated neoplasia.     

Dynamics of Hypoxic Zones in the Baltic Sea in the Late XX–Early XXI Century

Water Resources - The data of shipboard measurements of oxygen concentration at international monitoring stations in the Baltic Sea were used to assess the year-to-year variations of oxygen regime...     

Monitoring biological effects of pollution in the Baltic Sea: neglected--but still wanted?

In the Baltic Sea, studies regarding biological effects of contaminants are relatively few, partly due to political and economical reasons, specific hydrographic characteristics, and a strong eutrophication-targeted research focus during the past three decades. The development of a monitoring strategy concerning biological effects and its implementation into environmental monitoring programmes in the Baltic Sea is lagging behind the progress currently taking place in most of western and southern Europe. The pan-European project BEEP (Biological Effects of Environmental Pollution on Marine Coastal Ecosystems, 2001-2004) included the Baltic Sea as one of the target areas for the evaluation of a suite of biological effects indicators in European coastal waters. The main aims of the BEEP project are described and how the expected outcome for the Baltic Sea could provide the needed "baseline" information and expertise for a biological effect monitoring and contribute to harmonise environmental monitoring programmes within the EU.     

Biomarker responses in flounder (Platichthys flesus) and mussel (Mytilus edulis) in the Klaipeda-Būtinge area (Baltic Sea)

During the EU project BEEP a battery of biomarkers was applied in flounder (Platichthys flesus) and the blue mussel (Mytilus edulis) collected at three locations off the Lithuanian coast (Baltic Sea) in June and September 2001 and 2002. The elevated biomarker responses in specimens sampled in September 2001 were apparently related to the extensive dredging activities in the Klaipeda port area and subsequent dumping of contaminated sediments. High concentrations of organic pollutants (organochlorines and PBDEs) were also measured in the tissues of both indicator species. In addition, response levels of genotoxicity, cytotoxicity, immunotoxicity as well as concentrations of PAH metabolites in the bile of flounder showed elevations in 2002 after an oil spill in the Būtinge oil terminal in November 2001. In flounder, biomarker measurements 10 months after the spill indicated recovery processes but in mussels a high level of genotoxicity could still be observed 22 months later. The present study illustrates the usefulness of the multi-biomarker approach in the detection of biological effects of pollution in this region of the Baltic Sea.     

The effect of Razdol’naya River on the environmental state of Amur Bay (the Sea of Japan)

Seasonal variations in biogenic substances (nitrates, nitrites, ammonium, phosphates, and silicates), dissolved oxygen, dissolved organic matter, chlorophyll, humus, and suspended matter at seven stations on the Razdol’naya River are examined. Based on seasonal variations, the local sources of river water pollution by biogenic substances were identified. The annual and daily fluxes of biogenic substances through the Razdol’naya River into Amur Bay are calculated. A diffuse pollution source—agricultural fields in river valley—are shown to be the main source of biogenic substance fluxes. The vast hypoxia in the bottom water of Amur Bay, detected by the authors in 2007 and 2008, is supposed to be mostly caused by floods on the Razdol’naya R., which create favorable conditions of water blooming in Amur Bay in summer. The biomass of dead phytoplankton, experiencing microbiological decomposition and oxidation, causes hypoxia of bottom waters in the bay.     

Series of asymmetric pulses in the low-frequency range (Periods of 1–300 min) of microseisms as indicators of a metastable state in seismically active zones

Analysis of microseismic oscillations in a period range of several minutes recorded before the Kronotsky (December 5, 1997), Simushir (November 15, 2006), Hokkaido (September 25, 2003), and Neftegorsk (May 27, 1995) earthquakes revealed series of asymmetric pulses (SAPs) arising a few days before the earthquakes. Records of IRIS stations located at various distances from epicenters of the earthquakes were analyzed. SAPs were recorded only by stations located in a seismoactive zone in which an earthquake occurred. The SAP onset times and amplitudes are uncorrelated with the microseismic noise level in a period range of several seconds caused by storm phenomena in the ocean and other meteorological factors. Some intervals between successive pulses had the same length, which indicated a periodicity of their occurrence. It is supposed that SAPs can be caused by elastoplastic displacements in a fault zone.     

Assessment of water and bottom sediment conditions in the bights of Koz’mina and Lake Vtoroe (Nakhodka Gulf,Peter the Great Bay,the Sea of Japan)

The state of the water area in the Bays of Koz’mina and Lake Vtoroe (Nakhodka Gulf is evaluated. The data given include water temperature and salinity, biochemical oxygen demand, pH, alkalinity, chlorophyll a, organic matter, biogenic elements, oil products, detergents, polycyclic aromatic hydrocarbons, phenols, and organochlorine pesticides in water and bottom sediments. Pollutants may enter the system of bights from both onshore sources and the open part of the bay. The water and bottom sediments in this part of the bay show higher values of BOD5 and the concentrations of oil products, polycyclic aromatic hydrocarbons, phenols, and organochlorine pesticides. The anthropogenic load on the water body is shown to increase because of the new industrial construction on its shore.     

Dating the recent past (<500 years) by post-IR IRSL feldspar – Examples from the North Sea and Baltic Sea coast

The applicability of the post-IR IRSL single-aliquot regenerative-dose protocol (termed pIRIR protocol) has been tested on K-rich feldspar from recent coastal sediment samples (<500 a) from the southern North Sea coast and southern Baltic Sea coast. The most suitable post-IR IRSL (pIRIR) stimulation temperature is found to be 150 °C by using a preheat temperature of 180 °C. For this pIRIR stimulation temperature, a detectable pIRIR signal is obtained and the residual dose is minimized. Furthermore, anomalous fading is found to be negligible in the pIRIR₁₅₀ signal for our young samples whereas the fading rates for the conventional IRSL signal measured at 50 °C (IRSL₅₀) is between 5 and 7%/decade. However, the pIRIR₁₅₀ signal bleaches significantly slower compared to the IRSL_50, according to bleaching experiments using daylight, solar simulator and IR diodes, although the residual doses of both signals are similar. The laboratory residual doses in perfectly bleached aliquots are variable from sample to sample and vary between 300 ± 170 and 800 ± 460 mGy for the pIRIR₁₅₀. The precision of the residual dose determination is generally poor and causes large uncertainties on the residual subtracted ages. The laboratory residual doses alone cannot account for the observed overestimation in our two youngest samples (<70 a), indicating that the feldspar signals in these samples were presumably not fully bleached prior to aeolian or beach deposition. However, even if the age uncertainties are large we obtained pIRIR₁₅₀ ages in agreement with independent age estimates for the two older samples, which are 70 and 390 years old.     

Spatial variations of methane distribution in marine environment and its fluxes at the water–atmosphere interface in the western Sea of Okhotsk

Data of integrated gas-geochemical studies in the 45 cruise of the R/V Akademik M.A. Lavrent’ev in July 2008 were used to study the spatial distribution of methane in the surface seawater layer, the distribution and qualitative composition of hydrocarbon gases in bottom sediments of the northwestern continental shelf, northeastern slope of Sakhalin Island, and Deryugin depression in the Sea of Okhotsk. The specific features of the methane anomalies that form in this case are considered. Tectonic faults and the distribution of oil-and-gas-bearing structures are the main factors governing the formation of hydrocarbon gas fluxes in the study area. The surface water in the entire examined area was found to be oversaturated with methane. A developed model was used to calculated methane fluxes at the water–atmosphere interface and to identify areas with maximal fluxes (up to 324 mol/(km² day).