Seasonal variations in phosphorus species in the surface sediments of the Gulf of Riga, Baltic Sea.

The redox-dependent variations in concentrations of phosphorus at two different accumulation bottom areas were investigated in the Gulf of Riga (Baltic Sea) between December 1993 and January 1995. The sediment samples from nine sampling occasions were analyzed for phosphorus forms and redox potential. The average concentrations of total phosphorus measured in 0-1 cm (65 and 89 micromol P g(-1) for sites G5 and T3, respectively) were among the highest reported from the entire Baltic Sea. Redox-dependent "mobile" phosphorus (MP) contributed more than 50% of total in the uppermost-oxidized centimeter, whereas in reduced layers it was 16-18% throughout the year. The significant differences (ANOVA, P<0.01) among months of inorganic phosphorus (IP) concentration at 0-1 cm were observed at site G5 due to temporary accumulation of mobile phosphorus mediated by redox-dependent bacteria activity during summer. On the contrary no accumulation was observed at T3 probably as a result of low redox potential caused by high accumulation rates and low bioturbation. Although the water column above sediments remained oxic throughout the investigation period, the redox potential at site T3 was close to the redoxcline (i.e., +230 mV) during summer. Further increase of eutrophication might lead to development of anoxic conditions at sediment-water interface and that in turn will result in rapid release of redox-dependent phosphorus stored in surface sediments. The availability of excess phosphorus will further enhance eutrophication in partly phosphorus-limited Gulf of Riga.     

Seasonal variations of hydroxylated and methoxylated brominated diphenyl ethers in blue mussels from the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) found at high levels in the Baltic biota are mainly natural products, but can also be formed through metabolism or abiotic oxidation of polybrominated diphenyl ethers (PBDEs). The formation of OH-PBDEs is of concern since there is growing evidence of phenolic toxicity. This study investigates seasonal variations in levels of OH-PBDEs and MeO-PBDEs, focusing on an exposed species, the blue mussel (Mytilus edulis), sampled in the Baltic Sea in May, June, August and October of 2008. Both the OH-PBDE and MeO-PBDE levels in the mussels showed seasonal variations from May to October, the highest concentration of each congener appearing in June. The seasonal variation was more marked for OH-PBDEs than in MeO-PBDEs, but all congeners showed the same trends, except 6-MeO-BDE47 and 2′-MeO-BDE68, which did not significantly decline in concentrations after June. Biotic or abiotic debromination is suggested as a possible reason for the rapid decrease in methoxylated penta- and hexa-BDE concentrations observed in blue mussels from June to August, while the tetraBDE concentrations were stable. In addition, 1,3,7/1,3,8-tribrominated dibenzo-p-dioxins showed the same seasonal variation. The seasonal variations indicates natural formation and are unlikely to be due to transformation of anthropogenic precursors. The levels of PBDEs were fairly constant over time and considerably lower than those of the OH-PBDEs and MeO-PBDEs. The timing of the peaks in concentrations suggests that filamentous macro-algae may be important sources of these compounds found in the blue mussels from this Baltic Sea location.     

Contamination of River Kymijoki sediments with polychlorinated dibenzo-p-dioxins, dibenzofurans and mercury and their transport to the Gulf of Finland in the Baltic Sea

Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as the chemical industry. Up to 24,000 ton of wood preservative, chlorophenol known as Ky-5, was manufactured in the upper reaches of the river, an unknown amount of which was discharged into the river between 1940 and 1984. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurred as impurities in the final Ky-5 product. The PCDD/F concentrations and burden in the river sediments were studied and the transport of PCDD/Fs from contaminated sites downstream and into the Gulf of Finland in the Baltic Sea was estimated. More than 190 sediment cores were sampled to estimate the volume of contaminated sediments and the total PCDD/F burden. The transport of PCDD/Fs was estimated using sediment traps placed at several sites. The survey revealed that sediments in the river were heavily polluted by PCDD/Fs, the main toxic congener being 1,2,3,4,6,7,8-heptachlorodibenzofuran, a major contaminant in the Ky-5 product. The mean total concentration at the most polluted river site downstream from the main source was 42000 microg kg(-1) d.w. (106 microg I-TEQ kg(-1)). The elevated concentrations in the coastal region and the present estimated transport from the River Kymijoki confirm earlier assessments that the river is a major source of PCDD/F for the Gulf of Finland.     

Sedimentation of PCDD/Fs and PCBs in the Gulf of Finland and the Gulf of Bothnia,the Baltic Sea

Sediment trap material was collected during May–December in the period 1996–2008 in three coastal areas and four open sea stations in the Finnish territory of the Baltic Sea. The highest sedimentation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with a typical source-related congener profile from chlorophenol production dominated by highly chlorinated dibenzofurans was found close to a historical source in the Kymijoki estuary. This was an order of magnitude higher than in other river estuaries and two orders of magnitude higher than in the open sea stations. The sedimentation of polychlorinated biphenyls (PCBs) was also higher in river estuaries than in other areas. No significant decrease over a 12 year period of monitoring was found in concentration or in sedimentation in the Kymijoki estuary. In the western Gulf of Finland, the Archipelago Sea and the Gulf of Bothnia, the dominating congeners, calculated as toxic equivalent (TEQ) in sedimentation were 1, 2, 3, 7, 8-PeCDD and 2, 3, 4, 7, 8-PeCDF, often reported as the main congeners in deposition.     

Microplastic abundance in beach sediments of the Kiel Fjord,Western Baltic Sea

Environmental Science and Pollution Research - We assessed the abundance of microplastics (0.2–5&nbsp;mm) in drift line sediments from three sites in Kiel Fjord,&nbsp;Western Baltic...     

Seasonal and spatial distribution of metals in surface sediment of an urban estuary

Aquatic pollution by metals is of concern because of various toxic effects to marine life. The Tolka Estuary, Co. Dublin, Ireland, is a typical Irish urban estuary. It has a significant metal loading originating from the urban environment. Results of a 25month analysis of cadmium, copper, lead and zinc spatial and temporal distribution over 10 sample locations in this estuary are presented in this paper. Metal concentrations were analysed using differential pulse polarography. Significant seasonal and spatial trends in metal distribution were observed over the 25months. Sediment metal concentrations gradually increased (30-120%) in spring to a maximum at the end of summer which was followed by a decrease in winter months (30-60%). Sediment organic matter (OM) concentrations exhibited similar seasonal trends and a positive correlation between OM and metal distributions was observed, implying OM had an influence on metal distributions over time.     

Permanent seafloor anoxia in coastal basins of the northwestern Gulf of Finland, Baltic Sea

The Gulf of Finland is regularly affected by inflows of anoxic deep-water masses from the northern Baltic proper. These dense water masses advance over large areas with a decline of benthic life in affected areas as a result. Such events have been regularly repeated over decades and centuries. The archipelago, however, is well protected, because the inflows of anoxic deep waters do not enter such shallow waters. The situation could thus be better for benthic life in the archipelago, but in many areas this is not true. In areas where the bottoms are sheltered from storms and currents, permanent anoxia can persist for decades. Such areas were found in the western archipelago of the Gulf of Finland. Examination of surface cores revealed that many of these basins have been continuously anoxic for almost 40 years. A deeper coring showed that, at least locally, shallow water seafloor anoxia has been a fact in the area for thousands of years.     

Polychlorinated biphenyls and organochlorine pesticides in Baltic Sea sediments and bivalves

Insecticide resistance is an evolutionary response to insecticides and, as such, important for environmental biomonitoring and for pest management. Fitness disadvantage in the absence of insecticide is a frequent assumption in models of insecticide resistance evolution, which was observed in different insect species. Fitness studies are based in demographic performance of isolated populations without direct interaction between insecticide-resistant and -susceptible populations. Here we reported a study of direct competition following a factorial bivariate design between an insecticide-susceptible population of the maize weevil, Sitophilus zeamais Motschulsky (Coleoptera: Curculionidae), and one of two insecticide-resistant populations - one exhibiting fitness disadvantage based on demographic studies (Juiz de Fora) and other not exhibiting it (Jacarezinho). Total number of insects, mortality by insecticide, insect body mass and respiration rate were recorded after three generations of competition. Indeed, fitness disadvantage was observed in the resistant population from Juiz de Fora, but not in the population from Jacarezinho, as expected. The higher body mass and respiration rate of the insecticide-resistant insects from Jacarezinho are probably mitigating the physiological costs associated with the insecticide resistance minimizing their fitness disadvantage, what does not take place with the insecticide-resistant insects from Juiz de Fora. These distinct responses between the insecticide-resistant populations are probably related to the length and intensity of field-selection with insecticides.     

Seasonal and spatial distribution of nonylphenol in Shihwa Lake, Korea

Alkylphenols (APs) have been known as endocrine disruptors and consequently received much environmental concern. This study focused on seasonal variation and spatial distribution of nonylphenol (NP) in various matrixes including dissolved water, particulates, surface sediment, sediment trap and sediment core taken from Shihwa Lake and its adjacent areas. A total of 11 phenolic compounds including nonylphenol, t-octylphenol (t-OP) and bisphenol A (BPA) were measured in February, June and October 2002. NP is the most abundant chemical among the phenolic compounds and its concentrations in dissolved water, particulates and surface sediments from Shihwa Lake were measured as 17.4-1533.1 ng/l, 4.3-831.2 ng/l and 10.4-5054.1 ng/g dw, respectively. NP concentration in dissolved water varied with seasons and generally showed a decreasing order of June > October > February, while the seasonal trend was hardly found in sediment. High levels of NP were measured in surrounding industrial complexes, the concentrations was decreased gradually with distance from the industrial areas. NP in core samples showed an increasing trend toward the core depth. There exists a reasonable correlation between NP in dissolved water and in particulates, whereas the correlation between NP in dissolved water and in sediments is not significant. APs concentrations in Shihwa Lake were comparable to other highly polluted areas of the world and their possible effects on various organisms in the lake are discussed.     

A microcosm approach for evaluating the microbial nonylphenol and butyltin biodegradation and bacterial community shifts in co-contaminated bottom sediments from the Gulf of Finland,the Baltic Sea

Environmental Science and Pollution Research - Pollution of aquatic ecosystems with nonylphenol (NP) and butyltins (BuTs) is of great concern due to their effects on endocrine activity, toxicity to...     

Determination of some aliphatic and polycyclic aromatic hydrocarbons in marine sediments of the Baltic Sea

Two representative samples of surficial marine sediments have been studied, one from the northern Baltic Proper and the other from the Gulf of Finland. Aliphatic hydrocarbons were determined by gas chromatography on a fused silica capillary column, and six polyaromatic hydrocarbons were determined by gas chromatography-mass fragmentography. Hydrocarbons were extracted with a benzene-methanol mixture and ultrasonic agitation. The aliphatic hydrocarbons were tentatively identified by their retention times. The polyaromatic hydrocarbons (PAHs) were identified on the basis of their retention times and mass fragmentograms by direct comparison with those of standard compounds. The aliphatic hydrocarbon contents ranged from 0,1 to 2,6 μg/g dry matter. In both samples there was a clear maximum at n-C₁₇ and also a clear odd-carbon predominance. The PAH contents ranged from 4 to 120 ng/g dry matter. The PAH concentration was about 58 per cent higher in the sample from the Gulf of Finland than in the sample from the Baltic Proper.     

Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin,Southern Baltic Sea

The mercury compounds introduced to the environment because of anthropogenic activity are accumulated, mainly, in marine sediments. Both distribution of mercury in the Baltic Sea and factors affecting it are remain largely unknown. Due to its complex chemistry and variable conditions in the Baltic Sea bottom sediments, mercury may be reemitted to the overlaying water, and thus to the environment.The aim of this study was twofold. Total mercury contents were measured in sediments of the Gdansk Basin along a Vistula mouth (main source)--Gdansk Deep (deposition area) transect in order to assess spatial distribution of the element. Soft and sandy bottom sediment cores were collected and cut into slices. The mercury measurements consisted of acid digestion followed by CV-AAS determination. A five-step sequential extraction procedure involving measurements of mercury species water soluble, bound to humic substances and insoluble, was employed in order to investigate mercury speciation. On the basis of speciation results stability and remobilisation potential was assessed. The second aim was demonstrating that mercury gradients in vertical profiles of the investigated sediment cores exist.Total mercury contents varied in range from 28 ng/g x dw to 844 ng/g. Mercury associated with organic matter and sulphides, (respectively 39% and 49%) were the dominant species of the element. The results indicated that the river run-off is a source of mercury in the area. Vertical gradients of both total content and speciation of mercury in the soft sediments were attributed to both remobilisation from sediments, and decreasing trend in the anthropogenic load of the element deposited to sediments.     

Seasonal and spatial variations of Po and Pb activity concentrations in Mytilus galloprovincialis from Croatian coast of the Adriatic Sea

Results of 2 years monitoring of ²¹⁰Po and ²¹⁰Pb activity concentrations in soft tissue of the species Mytilus galloprovincialis from Croatian part of the Adriatic coast are presented. The samples were collected at thirteen coastal stations (some of which are also a part of the Mediterranean Mussel Watch Project) in spring and autumn of 2010 and 2011. The collected mussels were ranging between 4 cm and 6 cm in shell length. After sample pre-treatment lead and polonium were radiochemically separated on Sr resin. ²¹⁰Po was determined by alpha-particle spectrometry and ²¹⁰Pb was determined, via ²¹⁰Bi, by a low-level gas proportional counter. The results of ²¹⁰Po activity concentrations were found to vary between (104 ± 11) and (1421 ± 81) Bq kg⁻¹ dry weight while ²¹⁰Pb activity concentrations were much lower and in range (8.2 ± 5.3)–(94.1 ± 29.8) Bq kg⁻¹ dry weight. Higher ²¹⁰Po and ²¹⁰Pb activity concentrations were determined in spring period. The inter-site differences seen in their activity concentrations can be due to natural background levels of sites. The ²¹⁰Po/²¹⁰Pb activity concentration ratios in all cases exceeded unity for all mussel samples and ranged between 4.0 and 47.9.     

Evaluation of ecological risk,source, and spatial distribution of some heavy metals in marine sediments in the Middle and Eastern Black Sea region,Turkey

Environmental Science and Pollution Research - In the present study, the concentration levels of heavy metals such as Mn, Fe, Ni, Cu, Zn, Cr, and Pb in sediment samples collected from 16 sampling...     

PCDD/Fs in sprat (Sprattus sprattus balticus) from the Gulf of Finland, the Baltic Sea

The concentrations and congeners pattern of the polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in sprat collected by the commercial catches in the Gulf of Finland, Baltic Sea. Based on the toxic equivalent concentrations 2,3,4,7,8-PeCDF prevailed among the congeners of PCDD/Fs. The significance of age- and season-specific relationship between the concentration of lipids and dioxins was demonstrated. On lipid weight basis the concentration of PCDDs was significantly higher in spring than in autumn. This difference was not statistically significant for PCDFs. On lipid weight basis the concentration of dioxins decreased with rising content of lipids. PCDD/Fs toxic equivalent concentration increased with the age of sprat exceeding the EU maximum limit value at more than 5-year-old fish.     

On the leachability and sources of some elements in sediments from the Bothnian Sea and the Gotland Deep (the Baltic Sea)

The partitioning of some elements in sediments of two Baltic Sea basins (the Bothnian Sea and the Gotland Deep) was established by leaching experiments. Both partial (dithionite-citrate-bicarbonate) and "total" (HCl-KClO3) leach were used. Trace metals of both natural and anthropogenic sources (Co, Cu, Ni, Pb, Zn) were evaluated for affinity to terrestrial material and to authigenic mineral elements (Fe, S). The results indicate that the easily leachable "mobile" fraction is not necessarily a good indicator for pollution. Longer stagnation periods result in intensive pyrite formation in the Gotland Deep which mask pollution trends. The permanent oxic conditions in the Bothnian Sea may affect a dissolution capability for selected elements.     

Simulated sea surface temperature and heat fluxes in different climates of the Baltic Sea

The physical state of the Baltic Sea in possible future climates is approached by numerical model experiments with a regional coupled ocean-atmosphere model driven by different global simulations. Scenarios and recent climate simulations are compared to estimate changes. The sea surface is clearly warmer by 2.9 degrees C in the ensemble mean. The horizontal pattern of average annual mean warming can largely be explained in terms of ice-cover reduction. The transfer of heat from the atmosphere to the Baltic Sea shows a changed seasonal cycle: a reduced heat loss in fall, increased heat uptake in spring, and reduced heat uptake in summer. The interannual variability of surface temperature is generally increased. This is associated with a smoothed frequency distribution in northern basins. The overall heat budget shows increased solar radiation to the sea surface, which is balanced by changes of the other heat flux components.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Shell deformations in the Baltic clam Macoma balthica from southern Baltic Sea (the Gulf of Gdansk): hypotheses on environmental effects

High-resolution digital photography and graphical image analyses systems have been used to define external morphometric characters of shell deformations in four populations of the Baltic clam Macoma balthica from the Gulf of Gdansk (southern Baltic Sea). The proposed shell deformation indices (SDI), which were based on the relationship of selected dimensions in the posterior and the anterior part of the shell, showed at least three morphological features that provide a distinctive diagnosis of "regular" and "deformed" clams: the presence of flexure on the posterior side (SDI1), elongated posterior region (SDI2), and shell growth (SDI3). The degree and prevalence of deformed clams varied locally over space. Increase in percentage contribution of aberrated shells with depth, corresponding to oxygen depletion profile in the Gulf, suggests low oxygen concentrations as the main agent exerting a deforming influence. The observed morphological aberrations developed with age (size) of a bivalve, suggesting a long-term effect of causal factors, and were accompanied by lightening shell weight, possibly due to decalcification of previously deposited calcareous material during anaerobic metabolism. It is hypothesized that hypoxic/anoxic conditions and a subsequent presence of hydrogen sulfide on a deep organic-rich sea bottom induce shell form alterations that enable the pumping of oxygenated water from above the anoxic layer. Such a morphological modification highlights the functional significance of shell deformations in protective response to the ambient low-oxygen concentrations. Sediment organotin concentrations fall within moderate to high contamination range and, therefore, may also have an adverse impact on the shell form. DNA analyses of the fragment of mitochondrial gene cytochrome oxidase I (COI, 393 base pairs) showed homogenous genetic structure of regular and deformed clams, indicating that shell deformations in M. balthica are primarily driven by acclimatization to the ambient environmental conditions.     

Concentrations and spatial distribution of trace metals in mangrove sediments from the Brisbane River, Australia

Fifty surface sediment samples were collected from 12 transects through a mangrove woodland near the mouth of the Brisbane River, Australia. Samples were analyzed for 10 trace metals; measured concentrations (microg g(-1)) were: Cu 3.1-34.1; Pb 7.7-84.7; Zn 40.8-144.0; Ag nd-2.8; Cr 7.6-116.8; V 16.4-57.9; Mo 7.6-82.6; Ni 2.4-57.6; As nd-13.0; and Cd nd-2.0. Coefficients of variation ranged from 22-153%. Sediments were moderately contaminated, with Mo being enriched by up to thirty times background levels. Spatial variation was considerable, and canonical trend analysis showed concentrations of all metals but Ag and Cr tended to increase downshore, suggesting tidal deposition was important in determining metal concentrations. Silver and Cr concentrations appeared to be a consequence of contamination from landward point sources. An investigation of different random sampling intensities showed the spatial variation required that many samples be taken for a satisfactory assessment of metal burdens. Even so, mean values were not a good indication of the possible environmental effects of the metal contamination. Since metal concentrations increase downshore in inter-tidal environments, a more appropriate sampling strategy would be to take a downshore series of samples normal to the shoreline.