Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Fluxes of iron and manganese across the sediment–water interface under various redox conditions

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.     

Application of a mass-balance model to predict PCDD/F turnover in a Baltic coastal estuary

A dynamical, process-based mass-balance model was applied to quantify the transports of polychlorinated-p-dibenzodioxins and dibenzofurans (PCDD/Fs) to, within and from the Kallrigafjärden Bay, a coastal estuary in the Baltic Sea, and to predict the PCDD/F levels in the water and sediments of the bay. Before the modelling, a one-year sampling programme was implemented in 2007–2008 to measure the flows of PCDD/Fs in tributaries entering the system, the fluxes from the adjacent sea and the levels in water, sediment and fish within the estuary. The collected data set was used as input data to the model and for validation purposes.     

Environmental protection and the freedom of the high seas: The Baltic Sea as a PSSA from a Swedish perspective

In 2005, the Baltic Sea, except for its Russian waters, was designated as a particularly sensitive sea area (PSSA) by the International Maritime Organization (IMO). The previous designation of the Western European waters as a PSSA—intensely debated within the IMO—had repercussions for this process. Reviewing the case exposes the conflict between the fundamental principles, territorial sovereignty, and freedom of the high seas that international law seeks to balance. Likewise, review indicates that the PSSA concept is under almost constant reconceptualization as it is put to test in practice.     

Effects of water exchange and vegetation on the macroinvertebrate fauna composition of shallow land-uplift bays in the Baltic Sea

Shallow bays with soft sediment bottoms are common habitats along the Swedish and Finnish Baltic Sea coastline. These bays undergo a process of geomorphometric evolution with the natural isostatic land-uplift process, whereby open bays and sounds decrease in depth and are gradually isolated from the sea, forming bays with narrow openings. This study tested the relationship between the morphometric isolation of the bays from the sea and the macroinvertebrate fauna community of these bays. Additionally, we tested the specific role of the submerged vegetation as an indicator of the macroinvertebrate fauna community. We chose two environmental factors for the analyses, water exchange of the bays and the taxon richness of the macroflora in the bays. We found a hierarchical relationship between water exchange, flora taxon richness, and fauna biomass and taxon richness using structural equation modelling: decreased biomass and taxon richness of fauna were related to decreased flora taxon richness, which in turn was related to decreased water exchange. Using multivariate redundancy analysis, the two environmental factors included in the model were found to explain 47.7% of the variation in the fauna taxon composition and 57.5% of the variation in the functional feeding groups of the fauna. Along the morphometric isolation gradient of the bays, the fauna assemblages changed from a community dominated by gastropods, bivalves, and crustaceans, to a community mainly consisting of a few insect taxa. Moreover, the proportion of predators, gathering collectors, and shredders increased while that of filtering collectors and scrapers decreased. Our results indicate that the density and taxon richness of macroinvertebrate fauna are higher in less morphometrically isolated bays than in more isolated bays in the Baltic Sea. Furthermore, we suggest that the taxon richness of macroflora can serve as an indicator of the fauna community.     

Accumulation of total CO2 during stagnation in the Baltic Sea deep water and its relationship to nutrient and oxygen concentrations

Accumulation of total CO₂ (C_T) was investigated in the sub-halocline deep water of the Gotland Sea (Baltic Sea) during a period of stagnation from 1995 to 1999. Depth profiles for C_T, nitrate, phosphate, and oxygen were measured during seven cruises in a grid consisting of 26 stations. The mean C_T increased by more than 60 μmol/kg from October 1995 to July 1999 corresponding to a mean accumulation rate of 1.1 mol/m² year. Taking into account vertical mixing, the vertical distribution of the C_T accumulation was used to determine mineralization rates at different depths. High rates immediately below the halocline indicated the existence of a fraction of organic matter, which is rapidly mineralized during sinking through the water column. A second fraction is more refractive and accumulates at the sediment surface in the deep center of the basin where it is slowly mineralized and partly buried. Phosphate release rates in anoxic waters and especially at the redoxcline were substantially higher than those estimated on the basis of the carbon mineralization and the Redfield C/P ratio. This is attributed to non-Redfield mineralization ratios and the dissolution of iron oxide/phosphate associates. The formation of nitrate by mineralization under oxic conditions was almost completely compensated by denitrification. Using the carbon mineralization rates and a C/N ratio of 8.4, a denitrification rate of 280 mmol/m² year was obtained, which approximately balances the input of nitrate/ammonia into the surface water. Relating the apparent oxygen utilization (AOU) to the C_T fraction that was generated by mineralization yielded a carbon mineralization/O₂ consumption ratio of 0.83.     

Modelling surface drifting of buoys during a rapidly-moving weather front in the Gulf of Finland, Baltic Sea

The Gulf of Finland is an elongated estuary located in the north-eastern extremity of the Baltic Sea. This semi-enclosed sea-area is subject to heavy sea traffic, and is one of the main risk areas for oil accidents in the Baltic. The continuous development and validation of operational particle drift and oil-spill forecasting systems is thus seen to be essential for this sea-area.Here, the results of a three-day drift experiment in May 2003 are discussed. The field studies were performed using GPS-positioned surface floating buoys. The aim of this paper is to evaluate how well models can reproduce the drift of these buoys. Model simulations, both in forecast and hindcast modes, were carried out by three different 3D hydrodynamic models, the results of which are evaluated by comparing the calculated drifts with observations. These models were forced by HIRLAM (High Resolution Limited Area Model) and ECMWF (European Centre for Medium-Range Weather Forecasts) meteorological forecast fields.The simulated drift of the buoys showed a good agreement with observations even when, during the study period, a rapidly-changing wind situation was observed to affect the investigation area; in this situation the winds turned about 100 degrees in half an hour. In such a case it is a very complicated task to forecast the drifters' routes: there is a need to regularly update the meteorological forcing fields and to use these regularly-updated fields throughout the simulations. It is furthermore recommended that forecasts should be made using several circulation models and several meteorological forecasts, in order to get an overview of the accuracy of the forecasted drifts and related differences in between the forecasts.     

The past, present and future of the East/Japan sea in change: a simple moving-boundary box model approach

The East/Japan Sea is a mid-latitude marginal sea that has undergone dramatic changes during the last 50–60 years. One of the most prominent characteristics of these changes is a rapid decrease in the amount of dissolved oxygen in deep waters. As a consequence of these changes, some investigators have even argued that the East/Japan Sea might become an anoxic sea in the next 200 years. While the causes of these changes are still under investigation, it has been shown that they are mainly due to modifications in the mode of the deep water ventilation system in the East/Japan Sea: a slowdown and complete cessation of bottom water formation accompanied by an enhancement of upper water formation instead. A simple moving-boundary box model (MBBM) was developed in order to analyze and quantify the processes involved in such changes over the last 50–60 years. Using a MBBM, we estimated the levels of several conservative chemical tracers (CFCs, Tritium, SF₆, ¹³⁷Cs) and bioactive tracers (oxygen and phosphate) in the deep water masses of the East/Japan Sea, comparing these with the historical data available, and making predictions for the near future. The model predicts that the East/Japan Sea should remain well-oxygenated, despite recent rapid oxygen decreases in its deep waters, accompanied by such structural changes as a shrinking of its oxygen-depleted deeper waters and an expansion of its oxygen-rich upper waters over the next few decades.     

Comparison of benthic and pelagic suspension feeding in shallow water habitats of the Northeastern Baltic Sea

Combining field experiments with the biomass distribution data of dominant suspension feeders we compared the benthic and pelagic suspension feeding rates in shallow non-tidal brackish water coastal habitats. We found that pelagic grazing exceeded benthic grazing in almost all cases, on average from 14 to 4819 times depending on the site. Benthic grazing rates were related to site-specific environmental parameters and showed no relationship with water chlorophyl a (Chl a ) content, whereas pelagic grazing rates varied both spatially and temporally and were related to water Chl a content. Our results indicate that in several shallow coastal habitats, pelagic suspension feeding substantially exceeds benthic suspension feeding. This suggests that pelagic recycling is higher than the amounts of energy redirected from pelagic to benthic food webs by benthic suspension feeders. These results increase our knowledge of the energy flows in coastal ecosystems.     

Seasonal changes in the distribution and exchange of inorganic nitrogen between sediment and water in the Northern Baltic (Gulf of Bothnia)

The concentration profiles of nitrate plus nitrite, ammonium, and redox potential in sediment and water column were determined in late winter and summer at a sampling site off Norrbyn, northern Sweden, in the Gulf of Bothnia. The sediment had an oxidized surface layer during winter and spring, and nitrification occurred. Nitrate but not ammonium was present in the water column at this time. During summer a layer of planktonic detritus was deposited onto the sediment and led to its deoxygenation and reduction. Ammonium was then the predominant form of inorganic nitrogen in the water column.Laboratory experiments confirmed that nitrification in the surface layer of sediment prevented ammonium export during winter. Enhanced temperature or organic detritus deoxygenated the surface sediment and inhibited nitrification, and export of ammonium from the sediment increased. Although nitrification was important in determining the flow of nitrogen in the sediment it accounted for at most only 5% of the total oxygen uptake by the sediment.     

Time-series of surface water CO2 and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): Seasonality of uptake and release

High resolution measurements of carbon dioxide and oxygen were made in surface waters of the central Arkona Sea (Baltic Sea) from May 2003 to September 2004. Sensors for CO₂ partial pressure (pCO₂^w) and oxygen (O₂) concentration were mounted in 7 m depth on a moored platform which is used for hydrographic and meteorological monitoring. The pCO₂^w data were obtained in half hour intervals and O₂ was measured each hour as an average of a 10 min measurement. To check the performance of the sensors, pCO₂^w and O₂ were determined by shipboard measurements on a research vessel which visited the site in 1–2 month intervals. In addition, pCO₂^w was measured on a “volunteer observing ship” (VOS) passing the platform each second day at a distance of about 25 km. Minima of 220 to 250 μatm of pCO₂^w were observed at the time of the spring bloom and a cyanobacteria bloom in mid-summer. During winter the pCO₂^w was mostly close to equilibrium with the atmosphere but maxima of 430 to 530 μatm were also observed. The seasonality of oxygen and pCO₂^w showed an opposing pattern. From a multiple regression analysis, we concluded that two processes primarily controlled pCO₂^w during our study: biological turnover and mixing. A parameterization, based on apparent oxygen utilisation (AOU) and salinity (S) only (pCO₂^w = 1.23 AOU + 43 S), reproduced the seasonality of pCO₂^w in surface water reasonably well. Based on our pCO₂, salinity, and temperature data set, we attempted to separate processes changing total inorganic carbon concentrations (C_T) by using an alkalinity–salinity relation for the area. The contribution of CO₂ gas exchange and mixing were calculated and from this the biological turnover was deduced to reveal the calculated C_T changes.The net annual uptake of CO₂ in the central Arkona Sea was estimated to be about 1.5 Tg (1.5·10¹² g) which was approximately balanced by a net oxygen release considering the uncertainties of the flux calculations. Near-coast CO₂ emission due to episodic upwelling partly compensated the uptake of the central part of the Arkona Sea reducing the overall magnitude of the CO₂ uptake.     

海冰热力模式的辐射参数化方案在渤海和波罗的海应用的比较

研究了海冰热力模式中的各种辐射参数化方案,对比了模式计算的太阳短波辐射、大气长波辐射以及海冰热力变化,并利用渤海和波罗的海观测资料进行比较和误差分析.冬季大部分时间太阳短波辐射对海冰热力过程的作用有限.简单计算方案一般满足海冰模式要求.误差主要受云和冰雪表面与大气之间的多重反射影响.长波辐射对表面热平衡和海冰质量变化起重要作用.长波辐射参数化方案的计算结果受环境因素影响.云量参数化有待进一步改进.海冰模式计算结果的精度与长波辐射计算精度有一致性.     

The environmental effects of the installation and functioning of the submarine SwePol Link HVDC transmission line: a case study of the Polish Marine Area of the Baltic Sea

This paper describes the two-phase study of the environmental impact of the SwePol Link submarine electrical energy transfer system between Sweden and Poland. During the first phase (1997–1998), the potential effects of proposed technical solutions for the transmission line and different routes across the Baltic Sea were analysed. During the second phase (1999–2000), studies on environmental and background conditions before cable installation (1999) and studies on the environmental effects after cable system installation (2000) were undertaken. During this phase, underwater TV and video inspection of the bottom, observations of the bottom habitats by scuba-divers, sampling and laboratory analysis of macrozoobenthos and measurements of the earth's magnetic field were conducted.Underwater observations along the cable route indicated that one year after the cable had been laid no mechanical disturbances on the dynamic sandy bottom were visible. Studies of the bottom macrofauna indicated that there had been no significant changes in zoobenthos species composition, abundance or biomass which could have been clearly related to cable installation. Changes in the components of the magnetic field, although significant in the vicinity of the cable itself, did not exceed natural variability at a distance of 20 m.     

青岛─石岛近海反气旋中尺度涡旋存在证据及数值模拟

系统整理的历史实测海流和温盐资料显示出青岛─石岛近海水域全年都存在着中尺度反气旋式涡旋运动．利用二维数值模式,首次模拟出该涡旋的存在,并对这一涡旋的形成机制进行了探讨,数值模拟结果和实测吻合良好．数值计算表明：在冬季盛行风的作用下,山东半岛南岸出现减水,迫使北上的黄海暖流中的一部分向西北方向延伸,在到达山东半岛近海后向右转向,形成东北向沿岸流,这样,与绕过山东半岛大约沿40～50m等深线南下的黄海沿岸流作用,在青岛─石岛近海形成一个中尺度反气旋涡旋．夏季由于偏南风的作用,致使山东半岛南部近海浅水区域海水都向东北方向流动,与沿黄海冷水团锋面南下的黄海沿岸流相作用,由于流速切变也形成了上述涡旋．     

青岛-石岛近海反气旋中尺度涡旋存在证据及数值模拟

系统整理的历史实测海流和温盐资料显示出青岛-石岛近海水域全年都存在着中尺度反气旋式涡旋运动.利用二维数值模式,首次模拟出该涡旋的存在,并对这一涡旋的形成机制进行了探讨,数值模拟结果和实测吻合良好.数值计算表明:在冬季盛行风的作用下,山东半岛南岸出现减水,迫使北上的黄海暖流中的一部分向西北方向延伸,在到达山东半岛近海后向右转向,形成东北向沿岸流,这样,与绕过山东半岛大约沿40～50m等深线南下的黄海沿岸流作用,在青岛-石岛近海形成一个中尺度反气旋涡旋.夏季由于偏南风的作用,致使山东半岛南部近海浅水区域海水都向东北方向流动,与沿黄海冷水团锋面南下的黄海沿岸流相作用,由于流速切变也形成了上述涡旋.     

Spatial and temporal variations in the population structure of the soft-shell clam Mya arenaria in the Pomeranian Bay (southern Baltic Sea)

The population structure of Mya arenaria has been investigated in the sublittoral zone of the Pomeranian Bay (southern Baltic Sea). Box-corer samples were collected during a 1.5-year period in 1993/94 to follow changes in size and age structure of the clam populations in different parts of the study area. Large spatial differences in population structure were found between the sheltered southwest of the Bay and the shallow and exposed Oder Bank in the centre. The stock of the Oder Bank consisted of two different clam types. A slow-growing cohort was assumed to be autochtonous on the Oder Bank, whereas a fast-growing one was assumed to have immigrated from the surrounding area. The contribution of the two cohorts to the total density varied seasonally. Because of bedload transport of clams, the contribution to the reduction of the clam stock by wintering sea ducks could not be quantified. In the southwest of the Pomeranian Bay erosion was of minor importance. High mortality rates during the first two years of life were assumed to be caused by predation. Mortality rates of older cohorts remained stable until old age. Variations in cohort strength were related to interannual differences in the reproductive success. A mild winter presumably lowers the reproductive success in the subsequent summer. Severe oxygen depletion in summer 1994 caused a strong reduction in the clam stock at stations deeper than 10 m.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.