The distribution of artificial radionuclides in the English Channel, southern North Sea, Skagerrak and Kattegat, 1990–1993

This paper presents the initial results concerning the distribution of artificial radionuclides from research cruises conducted in collaboration by three European institutes as part of an EEC MAST research project. Ten cruises were undertaken covering the English Channel, southern and eastern North Sea, Skagerrak and Kattegat over a period of 2.5 yr. A large number of analyses of four artificial radionuclides (¹³⁷Cs, ⁹⁹Tc, ¹²⁵Sb, ⁹⁰Sr), which behave conservatively in seawater, provided information about the general distribution of water masses and circulation patterns as well as about single transport events in the study area. Controlled liquid releases from the La Hague nuclear fuel reprocessing plant are transported eastwards, forming a characteristic distribution pattern in the Channel and the southern North Sea. This includes a near-coastal “plume” and a distinct boundary between waters contaminated predominantly by La Hague and by Sellafield. Spatial and temporal distributions of radionuclide ratios were used, for the first time, to calculate transit times from the English Channel to the coast of Jutland. The data published herein provide an essential input to the calibration of numerical models simulating water transport processes. The results demonstrate the continuing usefulness of artificial radionuclides as oceanographic tracers, even at the very low concentrations observed at present in north-west European Shelf waters.     

Radioactive tracers as a tool in coastal oceanography: An overview of the MAST-52 project

Radionuclides (⁹⁹Tc, ¹²⁵Sb, ⁹⁰Sr, ¹³⁷Cs) discharged from La Hague in France have been used to trace advection and dispersion of water masses in the “European Coastal Current” from the English Channel to the Baltic. Time-series of radionuclide measurements in water samples taken in the English Channel, at the Netherlands coast, in the German North Sea sector and in Danish waters have been compared with reported discharge values. The prospects for using ¹²⁹I measured by accelerator mass spectrometry (AMS) as an oceanographic tracer have been evaluated as positive. The ⁹⁹Tc analytical procedure have been improved and background levels of ⁹⁹Tc, ¹³⁷Cs and ⁹⁰Sr in open North Atlantic seawater without influence from European discharges have been determined. An intercomparison programme have documented the quality of the measured ⁹⁹Tc and ¹²⁵Sb data. Transit times and transfer factors from La Hague to different locations in the study area have been estimated. It is concluded, that 10% of the La Hague discharge is transported through Kattegat and that 1/3 of the inflowing Kattegat bottom water originates from the coastal current. Three fundamentally different numeric models have been further developed under the project. The measured data have then been compared with values simulated by the three models. Models as well as measured data indicate, that a close coastal transport with longer transit times and often higher concentrations than seen in the open water main current is taking place. This coastal transport is important when contaminant transport is monitored. It is concluded, that the collected data gives a unique opportunity to evaluate models on advection and dispersion of coastal water masses and contaminants. The database will be made available as a tool for the evaluation of such models.     

Time series for sea water and seaweed of Tc and Sb originating from releases at La Hague

⁹⁹Tc and ¹²⁵Sb have been released in low level liquid waste at the reprocessing plant at La Hague (Fr). Over a number of years data have been obtained on the concentration of ⁹⁹Tc in sea water and in seaweed from sampling locations close to and at increasing distances north and east of the point of release into the English Channel.In addition such data have been obtained on ¹²⁵Sb for a small number of sampling points. These time series, and the information derived from their intercomparison and from comparison with the release data, are presented in this paper.Time series on ⁹⁹Tc as well as ¹²⁵Sb in sea water and seaweed clearly confirm a considerable decrease in release rates at La Hague over the years 1986–1993. Transit times and transfer factors derived from the series are generally in good agreement with the results of modelling efforts. The data do not provide evidence for a time lag between levels of the radionuclides in sea water and those in seaweed longer than a few months.The very high concentration factors for ⁹⁹Tc in brown seaweeds make these seaweeds very useful for environmental monitoring the radionuclide at low release rates and to trace releases in areas remote from the point of release.     

On the background level of Tc, Sr and Cs in the North Atlantic

Mean concentrations of the anthropogenic radioactive oceanographic tracers ⁹⁹Tc, ⁹⁰Sr and ¹³⁷Cs have been measured as 0.005, 1.6 and 2.5 Bq m⁻³ in oceanic Northeast Atlantic surface water, east and northeast of the Azores, in 1992. This is, apparently, the first published value for fallout “background” ⁹⁹Tc in oceanic Atlantic water.Comparison with older data indicates an observed half life for ⁹⁰Sr and ¹³⁷Cs in the northeast Atlantic surface water of 20 yr corresponding to a mean residence time of 80–100 yr for the stable elements.The observed ⁹⁹Tc/⁹⁰Sr ratio (3 × 10⁻³) in the Azores samples is 10 times higher than the theoretical fission yield decay corrected to 1992. This is in agreement with published data on rain water samples and may be characteristic for 1960's global fallout. Furthermore, the measured ¹³⁷Cs/⁹⁰Sr ratio is not significantly different from that observed for global fallout. There do not appear to be any additional significant sources of artificial radionuclides in this region.     

Transport of radionuclides by sea-ice and dense-water formed in western Kara Sea flaw leads

A transport assessment of particle-bound and dissolved artificial radionuclides (¹³⁷Cs and ^239,240Pu) by sea-ice and dense-water formed in western Kara Sea flaw leads close to the Novaya Zemlya dumping sites is presented in this study. We both performed a “best estimate” based on available data, and a “maximum assessment” relying on simulated constant releases of 1 TBq ¹³⁷Cs and ^239,240Pu from individual dumping bays. The estimates are based on a combination of (i) the content of particulate matter in sea-ice; (ii) analytical data and numerical simulations of radionuclide concentrations in shelf surface deposits, suspended particulate matter (SPM), and the dissolved phase; and (iii) estimates of lead-ice and dense-water formation rates as well as modeling results of local ice drift pathways. In the “best estimate” case, 2.90 GBq ¹³⁷Cs and 0.51 GBq ^239,240Pu attached to sea-ice sediments can be exported from the lead areas toward the central Arctic basin. The radionuclide burden of the annually formed dense lead water in the “best estimate” amounts to 4.68 TBq ¹³⁷Cs and 0.014 TBq ^239,240Pu. In the “maximum assessment”, potential export-rates of ice-particle bound ¹³⁷Cs and ^239,240Pu toward the central Arctic would amount to 0.64 and 0.16 TBq, respectively. As much as ≈900 TBq ¹³⁷Cs and ≈6.75 TBq ^239,240Pu could be annually taken up by 34.75 dense-water rejected in the lead area. Assuming the (unlikely) instantaneous release of the total ¹³⁷Cs and ^239,240Pu inventories (≈1 PBq and 10 TBq, respectively) from the Novaya Zemlya dumping sites into the dissolved phase, the dense lead water locally formed during one winter season could take up ≈90% of the Cs and ≈68% of the Pu released.     

Past, present and future state of the biogeochemical Si cycle in the Baltic Sea

The Baltic Sea is one of many aquatic ecosystems that show long-term declines in dissolved silicate (DSi) concentrations due to anthropogenic alteration of the biogeochemical Si cycle. Reductions in DSi in aquatic ecosystems have been coupled to hydrological regulation reducing inputs, but also with eutrophication, although the relative significance of both processes remains unknown for the observed reductions in DSi concentrations. Here we combine present and historical data on water column DSi concentrations, together with estimates of present river DSi loads to the Baltic, the load prior to damming together with estimates of the long-term accumulation of BSi in sediments. In addition, a model has been used to evaluate the past, present and future state of the biogeochemical Si cycle in the Baltic Sea. The present day DSi load to the Baltic Sea is 855 ktons y^− 1. Hydrological regulation and eutrophication of inland waters can account for a reduction of 420 ktons y^− 1 less riverine DSi entering the Baltic Sea today. Using published data on basin-wide accumulation rates we estimate that 1074 ktons y^− 1 of biogenic silica (BSi) is accumulating in the sediments, which is 36% higher than earlier estimates from the literature (791 ktons y^− 1). The difference is largely due to the high reported sedimentation rates in the Bothnian Sea and the Bothnian Bay. Using river DSi loads and estimated BSi accumulation, our model was not able to estimate water column DSi concentrations as burial estimates exceeded DSi inputs. The model was then used to estimate the BSi burial from measured DSi concentrations and DSi load. The model estimate for the total burial of BSi in all three basins was 620 ktons y^− 1, 74% less than estimated from sedimentation rates and sediment BSi concentrations. The model predicted 20% less BSi accumulation in the Baltic Proper and 10% less in the Bothnian Bay than estimated, but with significantly less BSi accumulation in the Bothnian Sea by a factor of 3. The model suggests there is an overestimation of basin-wide sedimentation rates in the Bothnian Bay and the Bothnian Sea. In the Baltic Proper, modelling shows that historical DSi concentrations were 2.6 times higher at the turn of the last century (ca. 1900) than at present. Although the DSi decrease has leveled out and at present there are only restricted areas of the Baltic Sea with limiting DSi concentrations, further declines in DSi concentrations will lead to widespread DSi limitation of diatoms with severe implications for the food web.     

FLUXMANCHE radiotracers measurements: A contribution to the dynamics of the English Channel and North Sea

From 1986 to 1992, ¹²⁵Sb released by the nuclear fuel reprocessing plant at La Hague has been used to study the transfer of waters from mid-Channel areas towards the Straits of Dover. Since 1940, these investigations have formed part of the MAST 53 FLUXMANCHE programme and have involved repeated measurements on a Straits of Dover transect. A discussion of the results is presented here which takes into account new information provided by a hydrodynamic model developed in the framework of FLUXMANCHE; it combines knowledge of the monthly fluxes of water trough the Straits of Dover and week-by-week simulation of the ¹²⁵Sb activities of waters flowing in this aera. It is proposed that soluble radionuclides introduced into the central Channel are transferred towards the Straits of Dover over a time which varies from four to seven months depending on the route taken.     

The trophic state of the Baltic Sea a century ago: a model simulation study

We apply a 3-D circulation model with a biogeochemical module (ERGOM) for the simulation of trophic conditions in the Baltic Sea a century ago. One aim is to provide reference or background data for nitrogen, phosphorus and chlorophyll, which is required for the implementation of the European Water Framework Directive (WFD). We assume that the situation a century ago serves this purpose well. Model input for this long-term simulation study are the regionally differentiated riverine and atmospheric nutrient loads to the Baltic Sea, which were compiled and calculated for a situation 100 years ago on the basis of various literature sources. For the mixed surface layer of the open Baltic Sea, we suggest maximum winter concentrations for dissolved phosphorus (dissolved inorganic nitrogen) of 0.23–0.35 (2.7–3.7) mmol/m³. Maximum chlorophyll-a concentrations are between 1.8 and 2.4 mg/m³. The concentrations of all parameters for different coastal waters vary in a wide range, depending on exposure to nutrient sources. Our nutrient concentrations for the situation a century ago are close to early measured data (1950–1960) and suggest that this data is suitable as reference data, as well.     

Changes in dissolved silicate loads to the Baltic Sea — The effects of lakes and reservoirs

We tested the hypothesis that dissolved silicate (DSi) yields [kg km^− 2 yr^− 1] of 82 major watersheds of the Baltic Sea can be expressed as a function of the hydraulic load (HL) as a measure of water residence time and the total organic carbon (TOC) concentration, both variables potentially increasing the DSi yield. Most boreal rivers fitted a linear regression model using HL as an independent variable to explain the DSi yield. Rivers with high HL, i.e., shortest residence times, showed highest DSi yields up to 2300 kg km^− 2 yr^− 1. This is most likely caused by an excess supply of DSi, i.e., the geochemical sources prevail over biological sinks in these boreal watersheds. The DSi yield for regulated and unregulated larger rivers of the boreal watersheds constituting about 40% of the total water discharge and of the total DSi load to the Baltic Sea, respectively, can be expressed as: DSi yield = 190 + 49.5 HL[m yr^− 1] + 0.346 TOC [µM] (R² = 0.80). Since both HL and TOC concentrations have decreased after damming, the DSi yields have decreased significantly in the regulated boreal watersheds, for the River Luleälven we estimated more than 30%. The larger eutrophic watersheds draining cultivated landscape of the southern catchment of the Baltic Sea and representing about 50% of the annual water discharge to the Baltic Sea, deviated from this pattern and showed lower DSi yields between 60–580 kg km^− 2 yr^− 1. DSi yields showed saturation curve like relationship to HL and it appears that DSi is retained in the watersheds efficiently through biogenic silica (BSi) production and subsequent sedimentation along the entire river network. The relationship between HL and DSi yields for all larger cultivated watersheds was best fitted by a Freundlich isotherm (DSi = 115.7HL¹⁰⁹; R² = 0.73), because once lake and reservoir area exceeds 10% of the watershed area, minimum DSi yields were reached. To estimate an uperturbed DSi yield for the larger eutrophic southeastern watersheds is still difficult, since no unperturbed watersheds for comparison were available. However, a rough estimate indicate that the DSi flux from the cultivated watersheds to the Baltic Sea is nowadays only half the uperturbed flux. Overall, the riverine DSi loads to the Baltic Sea might have dropped with 30–40% during the last century.     

Air–sea exchange of mercury vapour over the Gulf of Gda sk and southern Baltic Sea

The total gaseous mercury (TGM) in air over the coastal station at Hel and over the southern Baltic Sea was measured during the summer and winter conditions. Recorded 30-min resolution TGM data showed both higher concentrations and variability during the summer compared to the winter conditions. The summer TGM data ranged from 1.1 to 7.5 ng m⁻³, while the winter data ranged from 0.8 to 4.4 ng m⁻³. The TGM content in air over the southern Baltic Sea indicated that, in general, during the summer conditions, the sea-to-air transport of gaseous mercury dominated, while during the winter season, a tendency of gaseous mercury to sink into the water has been found. The evidences of enhanced water-to-air transfer of mercury vapour were noted, in particular, over the shallow waters of the Gulf of Gda sk under the strong water-to-air temperature gradients. Obtained results indicate that under such conditions, the coastal waters could act as a significant source of mercury vapour that may contribute to the overall budget of atmospheric mercury over the Baltic proper.     

Kinetic modelling of the dispersion of plutonium in the eastern Irish Sea: two approaches

A new model to simulate the dispersion of plutonium in the eastern Irish Sea is presented. The model solves the 3D hydrodynamic equations using normalized σ coordinates in the vertical simultaneously with the suspended matter equation. Pu can be present in three phases: water, suspended matter and bottom sediments. Reduction and oxidation reactions are also included in the model, in terms of reaction rates, since Pu can be present in the marine environment in principally two different oxidation states. Two kinetic models are presented to describe the transfers of radionuclides between the liquid and solid phases: a one-step model consisting of a single reversible reaction and a two-step model consisting of two consecutive reversible reactions. It has been found that both models can properly simulate the contamination of the waters and sediments from the eastern Irish Sea due to the releases from the BNFL Sellafield nuclear fuel processing plant, since the outputs from both models are very similar and in agreement with observations. Also, both models can simulate the speciation of Pu between the reduced and oxidized forms. However, if the dominant source of radionuclides to the water column is redissolution from a contaminated sediment, a process that is actually occurring in the Irish Sea, it has been found that a two-step model must be used. Indeed, a one-step model predicts the redissolution from the sediment to be unrealistically rapid.     

Carbon flows in Baltic Sea food webs — a re-evaluation using a mass balance approach

The brackish Baltic Sea has been seen as particularly suitable for studies of food webs. Compared to fully marine ecosystems, it has low species diversity, which means fewer trophic linkages to analyse. The Baltic Sea is also one of the best-studied areas of the world, suggesting that most data requirements for food web models should be fulfilled. Nevertheless, the influence of physical and biological factors on trophic interactions and biogeochemical patterns varies spatially in the Baltic Sea, adding considerable complexity to food web studies. Food web structure and processes can be described and compared quantitatively between areas by estimating the flow of matter or energy through the organisms. Most such models have been based on carbon, though studies of complementary flows of other elements limiting production, such as nitrogen and phosphorus would be desirable. However, since ratios between carbon and other elements are used in calculating these flows, it is crucial, as a first step, to quantify the flows of carbon as accurately as possible.In this study, we used the EcopathII software (ver 3.1) to analyse models of carbon flow through the food webs in the three main areas of the Baltic Sea; the Baltic proper, Bothnian Sea and Bothnian Bay. A previously published study on carbon flow in the Baltic Sea [Elmgren, R. 1984. Trophic dynamics in the enclosed, brackish Baltic Sea. Rapp. P.-V. Reun. — Cons. Int. Explor. Mer. (183) 152–169.] was complemented with the data on respiration and flow to detritus [Wulff, F., Ulanowicz, R. 1989. A comparative anatomy of the Baltic Sea and Chesapeeake Bay ecosystems. In: F. Wulff, J.G. Field, K.H. Mann (Eds.), Flow Analysis of Marine Ecosystems: Theory and Practice. New York: Springer-Verlag.] in order to present complete mass balance models of carbon. The purpose of re-evaluating previous models with new analytic tools was to check how well their carbon flows balance, and to provide a basis for improved mass balance models using more recent data, including nutrients other than carbon.The resulting mass balance networks for the Baltic proper, Bothnian Sea and the Bothnian Bay were shown to deviate from steady state. There was an organic carbon surplus of 45, 25 and 18 g C m⁻² year⁻¹ in the pelagic zones of the Baltic proper, Bothnian Sea and Bothnian Bay, respectively. The Ecopath network analysis confirmed that the overall carbon flow was highest in the Baltic proper, somewhat lower in the Bothnian Sea and much lower in the Bothnian Bay. The only clear differences in food web structure between the basins was that the average trophic level was lower for demersal fish in the Bothnian Sea and higher for macrofauna in the Bothnian Bay, compared to the other basins. The analysis showed weakness in our current understanding in Baltic Sea food webs and highlighted areas where improvements could be made with more recent data.     

Time series for dissolved cadmium at a coastal station in the Western Baltic Sea

Concentrations of dissolved Cd, Cd(diss), were measured weekly from June 1991 to June 1994 at a coastal station in the western Baltic Sea. The mean concentration of 204 pmol/dm³ is about 50% higher than in open Baltic Sea surface waters. A distinct seasonal cycle was observed with elevated concentrations in winter and spring (272 pmol/dm³) and lower values in summer and autumn (131 pmol/dm³). Relating the seasonal changes in Cd(diss) to the nutrient cycle revealed ΔCd(diss)/ΔNO₃ and ΔCd(diss)/ΔPO₄ ratios which are consistent with other measurements and seem to confirm the concept of a nutrient-like biogeochemistry of Cd. However, a time shift of two to three months exists between the depletion of nutrients in spring and the depletion of Cd(diss). Possibly, this indicates a decoupling of Cd(diss) from nutrients during the spring plankton bloom. However, no final conclusions can be drawn yet.Cd(diss) concentrations decreased significantly during the three year measurement period, whereas nitrate concentrations increased. A possible linkage between eutrophication and the Cd budget of the Baltic Sea is discussed.     

Biogeochemistry of sulfur in a sediment core from the west-central Baltic Sea: Evidence from stable isotopes and pyrite textures

The biogeochemistry of the sulfur cycle in a ca. 5-m-long sediment core from the eastern slope (221 m water depth) of the Landsort Deep in the west-central Baltic Sea was investigated by analyzing the solid phase records of sulfur isotopes and pyrite textures, besides selected main and minor elements. The sediments were deposited during post-glacial history of the Baltic Sea when the basin experienced alteration of brackish (Yoldia Sea, Littorina Sea) and freshwater (Baltic Ice Lake, Ancylus Lake) conditions. The stable isotopic composition of total sulfur was analyzed as a function of depth. In selected samples pyrite (FeS₂), greigite (Fe₃S₄), and barite (BaSO₄) fractions were separated for isotope analyses. Pyrite textures were analyzed by SEM and optical microscopy.Microbial reactions associated with the oxidation of organic matter resulted in assemblages of authigenic sulfide minerals which for the post-Ancylus Lake brackish water environment are dominated by pyrite and for freshwater environments by Fe-monosulfides. The sulfur isotopic composition of the brackish water Littorina Sea sediments (δ³⁴S between −40 and −27‰ vs. V-CDT) is believed to be determined by cellular sulfate reduction rates and reactions involving intermediate sulfur species. The availability of reactive iron and decomposable organic matter as well as sedimentation rate and the chemocline position are important variables upon the δ³⁴S values of sulfides in brackish water environment. The syn-depositional abundance of sulfur and organic matter, and transport of dissolved sulfur species vs. rates of microbial reactions determine δ³⁴S in the freshwater sediments. The upper part of the Ancylus Lake sediments is sulfidized by downward diffusing H₂S and/or sulfate from overlying brackish water sediments. Minor concretionary barite formation in the freshwater sediments is most likely due to the reaction of pore water sulfate diffusing downward from brackish water sediments with barium desorbed from freshwater sediments. The size distribution of pyrite framboids in the brackish sediments indicates that the formation mainly occurred from anoxic pore waters, although some pyrite formation in an anoxic water column cannot be excluded.     

Modern accumulation rates and a budget of sediment off the Gaoping (Kaoping) River, SW Taiwan: A tidal and flood dominated depositional environment around a submarine canyon

Ninety-two box cores collected during 2004–2006 from an area of ~ 3000 km² off the Gaoping (formerly spelled Kaoping) River, SW Taiwan, were analyzed for fallout radionuclides (²¹⁰Pb, ¹³⁷Cs and ⁷Be) to elucidate sedimentation rates and processes, and for the calculation of a sediment budget. The study area is located at an active collision margin with a narrow shelf and a submarine canyon extending essentially into the river's mouth. The results indicate fairly constant hemipelagic sedimentation in much of the open margin and for most of the time except in the inner shelf and along the axis of the canyon where sediment transport is more dynamic and is controlled by tidal current and wave activities constantly, and by fluvial floods or gravity-driven flows episodically. Sedimentation rates in the study area derived from ²¹⁰Pb and constrained by ¹³⁷Cs vary from 0.04 to 1.5 cm/yr, with the highest rates (> 1 cm/yr) flanking the Gaoping canyon over the upper slope (200–600 m) and the lowest rates (< 0.1 cm/yr) in the distal basin beyond the continental slope. The depocenter delineated from ²¹⁰Pb-based sedimentation rates overlaps with the area covered by a flood layer resulting from super-typhoon Haitang in July 2005. Such correspondence supports the notion that the processes operating on event timescale have bearing on the formation of the sediment strata over centennial or longer timescales.From the distribution of sedimentation rates, sediment deposited in the study area annually is estimated to be 6.6 Mton/yr, accounting for less than 20% of Gaoping River's sediment load. The calculated budget, coupled with the presence of the short-lived ⁷Be and non-steady-state distribution of low levels of ²¹⁰Pb in sediments along the canyon floor, suggests rapid transport of sediment from Gaoping River's mountainous watershed (the source) via the Gaoping (Kaoping) Submarine Canyon and adjacent channels (as the conduit and temporary sink) to the abyssal plain and the Manila Trench in the South China Sea (the ultimate sink).     

Resolving the impact of short-term variations in physical processes impacting on the spawning environment of eastern Baltic cod: application of a 3-D hydrodynamic model

Variations in oxygen conditions below the permanent halocline influence the ecosystem of the Baltic Sea through a number of mechanisms. In this study, we examine the effects of physical forcing on variations in the volume of deep oxygenated water suitable for reproductive success of central Baltic cod. Recent research has identified the importance of inflows of saline and oxygenated North Sea water into the Baltic Sea for the recruitment of Baltic cod. However, other processes have been suggested to modify this reproduction volume including variations in timing and volume of terrestrial runoff, variability of the solubility of oxygen due to variations in sea surface temperature as well as the influence of variations in wind stress. In order to examine the latter three mechanisms, we have performed simulations utilizing the Kiel Baltic Sea model for a period of a weak to moderate inflow of North Sea water into the Baltic, modifying wind stress, freshwater runoff and thermal inputs. The model is started from three-dimensional fields of temperature, salinity and oxygen obtained from a previous model run and forced by realistic atmospheric conditions. Results of this realistic reference run were compared to runs with modified meteorological forcing conditions and river runoff.From these simulations, it is apparent that processes other than major Baltic inflows have the potential to alter the reproduction volume of Baltic cod. Low near-surface air temperatures in the North Sea, the Skagerrak/Kattegat area and in the western Baltic influence the water mass properties (high oxygen solubility). Eastward oriented transports of these well-oxygenated highly saline water masses may have a significant positive impact on the Baltic cod reproduction volume in the Bornholm Basin.Finally, we analysed how large scale and local atmospheric forcing conditions are related to the identified major processes affecting the reproduction volume.     

Atmospheric emissions of European SECA shipping: long-term projections

We modeled the projections of the major atmospheric emissions from shipping of the European sulphur emission control area that includes the Baltic Sea, the North Sea, and the English Channel until 2040. Emission projections were calculated separately for every ship on annual basis, and the model took into account traffic growth, fleet renewal, and the forthcoming regulations. The regulation on sulfur content of ship fuels will drastically decrease the emissions of sulfur oxides and particulate matter (PM_2.5). As the regulation on nitrogen oxides (NO _x ) only affects the new diesel engines, the decrease in emissions will be seen parallel with the fleet renewal. Globally internalized limits will turn NO _x emissions to decrease with moderate traffic growth. However, by designating the Baltic Sea and the North Sea as NO _x emission control areas, more drastic decrease would occur. CO₂ emissions will stay almost constant through the studied timeline. Results show that European Commission's CO₂ target for 2050 will not be reached without implementation of market based measures among the North Sea and the Baltic Sea fleets. Results present new information for decision makers to further develop international regulations of shipping especially in the Baltic Sea and the North Sea.     

Diatom stratigraphy and long-term dissolved silica concentrations in the Baltic Sea

In many parts of the world coastal waters with anthropogenic eutrophication have experienced a gradual depletion of dissolved silica (DSi) stocks. This could put pressure on spring bloom diatom populations, e.g. by limiting the intensity of blooms or by causing shifts in species composition. In addition, eutrophication driven enhanced diatom growth is responsible for the redistribution of DSi from the water phase to the sediments, and changes in the growth conditions may be reflected in the sediment diatom stratigraphy.To test for changes in diatom communities we have analyzed four sediment cores from the Baltic Sea covering approximately the last 100 years. The sediment cores originate from the western Gulf of Finland, the Kattegat, the Baltic Proper and the Gulf of Riga. Three out of the four cores reveal only minor changes in composition of diatom assemblages, while the Gulf of Riga core contains major changes, occurring after the second World War. This area is set apart from the other Baltic Sea basins by a high frequency of low after spring bloom DSi concentrations (< 2 µmol L^− 1) during a relatively well defined time period from 1991–1998. In 1991 to 1993 a rapid decline of DSi spring concentrations and winter stocks (down to 5 µmol L^− 1) in the Gulf was preceded by exceptionally intense diatom spring blooms dominated by the heavily silicified species Thalassiosira baltica (1991–1992; up to 5.5 mg ww L^− 1). T. baltica has been the principal spring bloom diatom in the Gulf of Riga since records began in 1975. DSi consumption and biomass yield experiments with cultured T. baltica suggest that intense blooms can potentially exhaust the DSi stock of the water column and exceed the annual Si dissolution in the Gulf of Riga. The phytoplankton time series reveals another exceptional T. baltica bloom period in 1981–1983 (up to 8 mg L^− 1), which, however, took place before the regular DSi measurements. These periods may be reflected in the conspicuous accumulation of T. baltica frustules in the sediment core corresponding to ca. 1975–1985.     

Environmental changes and the responses of the ecosystems of the Yellow Sea during 1976–2000

The changes in the environmental features of the Yellow Sea during the last 25 years of the 20th century were studied using a set of seasonally monitored data along a transect (at 36°N) maintained by the State Oceanic Administration of China. The data included the ocean temperature (T), salinity (S) and biogenic elements, such as dissolved oxygen (DO), phosphorus (PO₄-P), silicon (SiO₃-Si) and dissolved inorganic nitrogen (DIN).The seasonal (summer and winter) values and the annual mean of these elements showed significant changes during the monitored period. Time series of T, S, DIN and N:P ratios exhibited positive trends, while those of DO, P and Si exhibited negative trends. During this period, the annual mean of T and DIN in the Yellow Sea increased by 1.7 °C and 2.95 μmol L⁻¹, respectively, while those of DO, P and Si decreased by 59.1, 0.1 and 3.93 μmol L⁻¹, respectively. In the 1980s, particularly in between 1985 and 1989, concentrations of P and Si dropped to near the ecological threshold for growth of diatoms. The N:P ratio increased from 4 in 1984 to over 16 in 2000. The climate trend coefficients, R_xt, for these time series are all above 0.43 with significance levels of 95%, except for salinity. The increases in T were consistent with the recent climate warming in northern China and the adjacent seas, i.e. the Bohai Sea and the East China Sea. The reduction of DO was probably attributable to the increase in T and decrease in primary production in these regions. The positive trend of DIN was mainly attributable to precipitation and partly to Changjiang River discharge. The negative concentration trends of P and Si were due to the decreases in their concentrations in seawater that flowed to the Yellow Sea from the Bohai Sea. As a result, N:P ratios greatly increased in the seawater of the Yellow Sea.Moreover, some important responses of the Yellow Sea ecosystems to the changes in physical variables and chemical biogenic elements were obviously displayed. These responses include strengthening nutrient limitation, decreasing chlorophyll a, primary production and phytoplankton abundance, succession of dominant phytoplankton species from diatoms to non-diatoms, changes in fish community structure and species diversity.     

Silicon dynamics in the Oder estuary, Baltic Sea

Studies on dissolved silicate (DSi) and biogenic silica (BSi) dynamics were carried out in the Oder estuary, Baltic Sea in 2000–2005. The Oder estuary proved to be an important component of the Oder River–Baltic Sea continuum where very intensive seasonal DSi uptake during spring and autumn, but also BSi regeneration during summer take place. Owing to the regeneration process annual DSi patterns in the river and the estuary distinctly differed; the annual patterns of DSi in the estuary showed two maxima and two minima in contrast to one maximum- and one minimum-pattern in the Oder River. DSi concentrations in the river and in the estuary were highest in winter (200–250 μmol dm^− 3) and lowest (often less than 1 μmol dm^− 3) in spring, concomitant with diatom growth; such low values are known to be limiting for new diatom growth. Secondary DSi summer peaks at the estuary exit exceeded 100 μmol dm^− 3, and these maxima were followed by autumn minima coinciding with the autumn diatom bloom. Seasonal peaks in BSi concentrations (ca. 100 μmol dm^− 3) occurred during the spring diatom bloom in the Oder River. Mass balance calculations of DSi and BSi showed that DSi + BSi import to the estuary over a two year period was 103.2 kt and that can be compared with the DSi export of 98.5 kt. The difference between these numbers gives room for ca. 2.5 kt BSi to be annually exported to the Baltic Sea. Sediment cores studies point to BSi annual accumulation on the level of 2.5 kt BSi. BSi import to the estuary is on the level of ca. 10.5 kt, thus ca. 5 kt of BSi is annually converted into the DSi, increasing the pool of DSi that leaves the system. BSi concentrations being ca. 2 times higher at the estuary entrance than at its exit remain in a good agreement with the DSi and BSi budgeting presented in the paper.