Long-term development of inorganic nutrients and chlorophyll alpha in the open northern Baltic Sea

Eutrophication is an ongoing process in most parts of the Baltic Sea. This article reports on the changes during recent decades of several eutrophication-related variables in the open sea areas surrounding Finland (wintertime nutrient concentrations, wintertime nutrient ratios, and summer time chlorophyll alpha concentrations at the surface). The sum of nitrate- and nitrite-nitrogen ([NO3+NO2]-N) was observed to increase nearly fourfold in the Northern Baltic Proper and the Gulf of Finland and almost double in the Bothnian Sea from the 1960s until the 1980s or 1990s. The increase was followed by a decrease, which was modest in the two former subregions. Phosphate-phosphorus (PO4-P) concentrations followed a similar pattern in the Northern Baltic Proper (threefold increase and subsequent slight decrease) and Bothnian Sea (30% increase and subsequent decrease), but increased throughout the study in the Gulf of Finland, with the present concentration being threefold to the measurements made in the early 1970s. The PO4-P concentration decreased throughout the study in the Bothnian Bay. Silicate-silicon (SiO4-Si) concentrations decreased 30-50% from the early 1970s to the late 1990s and increased 20-40% thereafter in the Northern Baltic Proper, the Gulf of Finland, and the Bothnian Sea. Chlorophyll alpha showed an increase of over 150% in the Northern Baltic Proper and the Gulf of Finland from the 1970s until the early 2000s. In the Bothnian Sea the chlorophyll alpha concentration increased more than 180% from the late 1970s until the late 1990s, and decreased thereafter. According to these long-term observations, the Gulf of Finland and Northern Baltic Proper show clear signs of eutrophication, which may be emphasized by hydrographical changes affecting the phytoplankton communities and thus the algal biomass.     

Simulated distributions of Baltic Sea-ice in warming climate and consequences for the winter habitat of the Baltic ringed seal

Sea-ice in the Baltic Sea in present and future climates is investigated. The Rossby Centre Regional Atmosphere-Ocean model was used to perform a set of 30-year-long time slice experiments. For each of the two driving global models HadAM3H and ECHAM4/OPYC3, one control run (1961-1990) and two scenario runs (2071-2100) based upon the SRES A2 and B2 emission scenarios were conducted. The future sea-ice volume in the Baltic Sea is reduced by 83% on average. The Bothnian Sea, large areas of the Gulf of Finland and Gulf of Riga, and the outer parts of the southwestern archipelago of Finland will become ice-free in the mean. The presented scenarios are used to study the impact of climate change on the Baltic ringed seal (Phoca hispida botnica). Climate change seems to be a major threat to all southern populations. The only fairly good winter sea-ice habitat is found to be confined to the Bay of Bothnia.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.     

Denitrification in the river estuaries of the northern Baltic Sea

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.     

Levels of PCDD/F and dioxin-like PCB in Baltic fish of different age and gender

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) in Baltic Sea fish like herring (Clupea harengus membras), sprat (Sprattus sprattus balticus), perch (Perca fluviatilis), pikeperch (Sander lucioperca) and flounder (Platichthys flesus trachurus) collected from four areas of the Estonian coastal waters are reported. All samples are studied for their relationship between the length (cm) and wet weight (g); length (cm) and age (years); lipid content and dry matter. The level of PCDD/F and PCB concentrations in younger 1-5 years old Baltic herring and sprat collected in 2002-2005 from the eastern and central parts of the Gulf of Finland, Gulf of Riga and Open Baltic Sea (Central Baltic) is related to the fish age and compared with those found in the 1990s. In addition, PCDD/F and PCB concentrations of different age groups herring, sprat, perch, pikeperch and flounder collected in 2003-2004 from the Lake Peipsi, Gulf of Finland, Gulf of Riga and Open Baltic Sea are related also to their age. Consequently, it was manifested that in older Baltic fish the concentrations of PCDD/F and PCB were higher than in the younger age groups. By the help of principle component analysis (PCA) the effect of gender on the concentrations of PCDD/F for the juvenile Baltic herring and sprat collected in 2004-2005 is investigated for the first time. It was summarized that the biological factor age plays a large role for the contamination of the fish with important toxic organohalogenated compounds such as PCDD/F.     

A North Sea and Baltic Sea Model Ensemble Eutrophication Assessment

A method to combine observations and an ensemble of ecological models is suggested to produce a eutrophication assessment. Using threshold values and methodology from the Oslo and Paris Commissions (OSPAR) and the Helsinki Commission (HELCOM), four models are combined to assess eutrophication for the Baltic and North Seas for the year 2006. The assessment indicates that the entire southeastern part of the North Sea, the Kattegat, the Danish Straits, the Gulf of Finland, and the Gulf of Riga as well as parts of the Arkona Basin, the Bornholm Basin, and the Baltic proper may be classified as problem areas. The Bothnian Bay and parts of the Baltic proper, the Bornholm Basin, and the Arkona Basin are classified as potential problem areas. This method is a useful tool for the classification of eutrophication; however, the results depend on the threshold values, and further work is needed within both OSPAR and HELCOM to harmonize these values.     

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011–2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069–2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air–sea gas exchange and “bulk” (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year^?1 for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year^?1 for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.     

Climate Warming and Pikeperch Year-Class Catches in the Baltic Sea

Climate change scenarios concerning the Baltic Sea predict increase in surface water temperatures. Pikeperch (Sander lucioperca (L.)) inhabits the coastal areas of the northern Baltic Sea and is an important fish species for the Finnish fisheries. The year-class strength of pikeperch varies strongly between years and significantly depends on water temperature. We aimed to study the effects of changing temperature conditions on pikeperch fisheries and distribution based on commercial catch data from the period 1980–2008 in the Finnish coastal areas of the Baltic Sea. The results indicated that warmer summers will produce stronger pikeperch year-classes that consequently contribute significantly to the future catches. The average temperature in June–July explained 40% of the variation in the year-class catches in the Gulf of Finland and 73% in July–August in the Archipelago Sea. During the study period, the distribution of pikeperch catches expanded toward north along the coasts of the Bothnian Sea.     

Cyclic volatile methylsiloxanes in fish from the Baltic Sea

Laboratory studies suggest that the cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) will persist in the aquatic environment and bioaccumulate in fish. Here these cVMS were measured in herring collected in the Swedish waters of the Baltic Sea and the North Sea and in grey seals from the Baltic Proper. D4, D5, and D6 were present in herring muscle at concentrations around 10, 200, and 40 ng g⁻¹ lipid weight, respectively. The ratio of these concentrations was similar to the relative magnitude of estimated emissions to water, suggesting that the efficiency of overall transfer through the environment and food web was similar (within a factor 2–3) for the three chemicals. The concentrations of D5 and D6 were similar in herring caught in the highly populated Baltic Proper and in the less populated Bothnian Sea and Bothnian Bay. The D4 concentrations were lower at the most remote northern station, suggesting that D4 is less persistent than D5 and D6. Herring from the North Sea had lower levels of all three chemicals. The concentrations of D4, D5 and D6 in grey seal blubber were lower than the lipid normalized concentrations in herring, indicating that they do not biomagnify in grey seals.     

Dioxin concentrations in sediments of the Baltic Sea--a survey of existing data

Recent survey results for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins) in Baltic Sea sediments from Finland, Sweden and Denmark were merged with previously published Baltic Sea data. Regional distribution of concentration levels, differences in congener patterns, and temporal changes in sediment profiles were examined. One of the main objectives was to study if any major point sources for different PCDD/F congeners could be identified on a regional scale, based on sediment records. The survey confirmed the impact of chlorophenol production derived highly chlorinated PCDF-congeners on the total toxicity in sediments in the Gulf of Finland near the Kymijoki river estuary. Signatures of other point sources or combined point sources pertinent to specific industry branches or particular production processes (such as pulp bleaching, vinyl chloride production, thermal processes) may be discerned. However, the findings did not support any of the known point sources significantly influencing those congeners that are most abundant in Baltic herring and salmon. Instead, regional distributions in the Baltic Sea indicate that atmospheric deposition may act as a major source for those congeners and especially for 2,3,4,7,8-PeCDF. There were clear indications of declines in levels in sediment in some areas, but generally the levels of highly chlorinated PCDD/Fs on the northern coast of the Gulf of Finland were still high when compared with other areas of the Baltic Sea. Major areas with data gaps cover the south-eastern and eastern coastal regions of the Baltic Proper and the southern Gulf of Finland.     

Searching efficient protection strategies for the eutrophied Gulf of Finland: the combined use of 1D and 3D modeling in assessing long-term state scenarios with high spatial resolution

An experiment combining the use of two ecosystem models was conducted to search for effective protection strategies for the Gulf of Finland (Baltic Sea). Reference and scenario simulations were first run with a one-dimensional (1D) model for seven main basins of the entire Baltic Sea until steady state was achieved. The obtained basinwise distributions of inorganic nitrogen (N) and phosphorus (P), as well as sediment labile P, were then used to initiate 5-y simulations with a three-dimensional (3D) ecosystem model. The results suggest that relatively small local load reductions (the "Finland" scenario) would improve only the state of adjacent coastal waters significantly. This would be the case, even for runs covering several decades, which clearly exceed the residence times of nutrients in the Gulf of Finland. A significant decrease from a substantial loading source to the Gulf (the "St. Petersburg" scenario) would decrease cyanobacterial biomasses in the entire Gulf of Finland and also immediately outside it. A reduction in the current Polish nutrient loads would improve the situation in the whole Baltic Proper and cause an extensive decline in cyanobacterial biomasses in the Gulf of Finland, as well. However, it would take several decades until the improvement caused by reducing loads in the "Poland" scenario is seen, while in the "St. Petersburg" scenario the corresponding time lag would only be a few years. Our results suggest that the common water protection policy in the Baltic Sea region should have the largest nutrient sources as its primary target, regardless of their location and country.     

The Effects of Hypoxia on Sediment Nitrogen Cycling in the Baltic Sea

Primary production in the eutrophic Baltic Sea is limited by nitrogen availability; hence denitrification (natural transformation of nitrate to gaseous N₂) in the sediments is crucial in mitigating the effects of eutrophication. This study shows that dissimilatory nitrate reduction to ammonium (DNRA) process, where nitrogen is not removed but instead recycled in the system, dominates nitrate reduction in low oxygen conditions (O₂ <110 μM), which have been persistent in the central Gulf of Finland during the past decade. The nitrogen removal rates measured in this study show that nitrogen removal has decreased in the Gulf of Finland compared to rates measured in mid-1990s and the decrease is most likely caused by the increased bottom water hypoxia.     

Concentrations of cadmium and other metals in Fucus vesiculosus L. and Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea

Concentrations of Cd and ten other metals (Al, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn) were determined in the brown seaweed Fucus vesiculosus L. and the aquatic moss, Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea. Elevated concentrations of metals were found in samples taken close to densely populated areas, such as Stockholm and Nyn?shamn. Very high concentrations of especially Zn were found in both Fucus and Fontinalis samples taken from the area south of the Gulf of G?vle. The results indicate that mining and industrial activities along the river Dal?lven are the main sources of Zn and several other metals. Cd concentrations in Fucus plants reached maximum values (24.5 mg kg(-1)) at the northern site. The gradual increase of Cd concentrations in Fucus plants northward could not be totally explained by the salinity gradient in the Baltic Sea; reasons for this are discussed in this paper.     

Relationships between colored dissolved organic matter and dissolved organic carbon in different coastal gradients of the Baltic Sea

Due to high terrestrial runoff, the Baltic Sea is rich in dissolved organic carbon (DOC), the light-absorbing fraction of which is referred to as colored dissolved organic matter (CDOM). Inputs of DOC and CDOM are predicted to increase with climate change, affecting coastal ecosystems. We found that the relationships between DOC, CDOM, salinity, and Secchi depth all differed between the two coastal areas studied; the W Gulf of Bothnia with high terrestrial input and the NW Baltic Proper with relatively little terrestrial input. The CDOM:DOC ratio was higher in the Gulf of Bothnia, where CDOM had a greater influence on the Secchi depth, which is used as an indicator of eutrophication and hence important for Baltic Sea management. Based on the results of this study, we recommend regular CDOM measurements in monitoring programmes, to increase the value of concurrent Secchi depth measurements.     

Organochlorine compounds in the Gulf of Bothnia: sediment and benthic species

Surface sediment, amphipods (Monoporeia affinis), isopods (Saduria entomon) and fourhorn sculpins (Oncocottus quadricornis) were collected at two coastal stations in the Gulf of Bothnia, one in the Bothnian Bay and the other in the Bothnian Sea. The objective was to study the concentrations, composition profiles, bioaccumulation features and spatial differences of organochlorine compounds such as hexachlorocyclohexanes (HCHs), DDTs, hexachlorobenzene (HCBz), chlordanes (CHLs), dieldrin, Mirex and polychlorinated biphenyls (PCBs). All groups of compounds were found in every sample investigated, with the exception of Mirex that was not detected in the sediment samples. The concentrations for e.g. PCBs and CHLs ranged from 700 to 2400 and 70 to 400 ng/g lipid in the specimens. For the corresponding sediments the results were 9.0-9.3 ng/g dw for PCBs and 0.54-0.57 ng/g dw for CHLs, respectively. Bioaccumulation differences between the species with regard to both degree of and type of compound were observed. The highest accumulation potential was found for the cyclodiene compounds including CHLs and Mirex in isopod. Finally, there were only small concentration and bioaccumulation differences between the two stations.     

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.     

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.     

Nitrogen fixation estimates for the Baltic Sea indicate high rates for the previously overlooked Bothnian Sea

Dense blooms of diazotrophic filamentous cyanobacteria are formed every summer in the Baltic Sea. We estimated their contribution to nitrogen fixation by combining two decades of cyanobacterial biovolume monitoring data with recently measured genera-specific nitrogen fixation rates. In the Bothnian Sea, estimated nitrogen fixation rates were 80 kt N year⁻¹, which has doubled during recent decades and now exceeds external loading from rivers and atmospheric deposition of 69 kt year⁻¹. The estimated contribution to the Baltic Proper was 399 kt N year⁻¹, which agrees well with previous estimates using other approaches and is greater than the external input of 374 kt N year⁻¹. Our approach can potentially be applied to continuously estimate nitrogen loads via nitrogen fixation. Those estimates are crucial for ecosystem adaptive management since internal nitrogen loading may counteract the positive effects of decreased external nutrient loading.     

Trace metals in flounder, Platichthys flesus (Linnaeus, 1758), and sediments from the Baltic Sea and the Portuguese Atlantic coast

Trace metals were examined in the muscle tissue of flatfish species of flounder, Platichthys flesus (Linnaeus, 1758), sediments from two southern Baltic Sea sites (Gdańsk Bay and Ustecko-?ebskie as a reference) and in two areas of the Portuguese Atlantic coast (Douro River estuary and Atlantic fishing ground as a reference) to evaluate spatial differences in trace metals. Additionally, the accumulation of trace metals in flounder of different length classes was assessed. Flounder from the Gdańsk Bay area contained twofold more cupper (Cu), lead (Pb) and mercury (Hg) than did flounder from the Douro River estuary, but zinc (Zn) and cadmium (Cd) were at similar concentrations. The sediments from Gdańsk Bay contained significantly more Zn and threefold more Cd, while concentrations of Cu and Pb were twofold lower. The concentrations of metals in the sediments did not correlate with those in the flounder. Spatial differences were noted in metal concentrations in flounder from the southern Baltic Sea and the Portuguese Atlantic coast as well as within these regions, with higher concentrations in the flounder from the Baltic Sea Gdańsk Bay. The flounder in length class 25–30 cm from Gdańsk Bay contained metal concentrations comparable to those of class 40–45 cm specimens from the Atlantic coast. The accumulation of metals in flounder length classes differed in the two regions.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in the general population in Finland

We measured adipose tissue concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs) in 420 general Finns living in southern Finland. The mean (median) concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 29.0 (24.1) and 20.7 (16.7) pg g-1 fat, respectively. The concentrations clearly correlated with age. Expressing the concentrations as a function of subject's ages revealed that the exposure of Finns has declined over the last 30 years. A downward gradient was found in the concentrations from the Baltic Sea coast to inland areas in Finland, and this was assessed to be due to consumption of the Baltic Sea fish, especially Baltic herring. Linear regression models for natural logarithm WHO(PCDD/F)-TEQ, natural logarithm WHO(PCB)-TEQ, and natural logarithm WHO(total)-TEQ, explained 70%, 69%, and 72% of the variability, respectively. Age, lactation, place of residence, and fish consumption frequencies were significant predictors in the models.