Geochemical characterization of recent sediments in the Baltic Sea by bulk and electron microprobe analysis

Nineteen samples of silty and clayey sediments of the Baltic Sea were analyzed by bulk methods (atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry), as well as by electron probe X-ray microanalysis (EPXMA). Processing of the EPXMA-data resulted in nine different particle types which have been identified as different mineral species. Quartz and aluminosilicate particles are most abundant (often more than 95%), although they are not of much help for the characterization of the geochemistry of Baltic sediments. Reduction products, such as Fe-sulfides and rhodochrosite, are found in anoxic sediment environments (e.g. Gotland Deep). The oxides/hydroxides of iron and manganese are more indicative of oxic environments (e.g. Kattegat). In regions with periodic changes in the redox conditions, oxides/hydroxides and sulfides are detected side by side (e.g. Lübeck Bight, Arkona Basin). The detected Ca- and Ti-rich particles show a geographical dependence. The Ca-rich particles are found in the transition region between the Baltic Sea and the North Sea. Ti-rich particles have high abundances around the coastlines of Germany (e.g. Lübeck Bight) and southern Poland. The results of the bulk analysis and of the individual particle analysis are often complementary.     

Modeling the pathways and ages of inflowing salt- and freshwater in the Baltic Sea

A three-dimensional, eddy-permitting ocean circulation model with implemented bottom boundary layer model and flux-corrected transport scheme is used to calculate the pathways and ages of various water masses in the Baltic Sea. The agreement between simulated and observed temperature and salinity profiles of the period 1980–2004 is satisfactory. Especially the renewal of the deep water in the Baltic proper by gravity-driven dense bottom flows is better simulated than in previous versions of the model. Based upon these model results details of the mean circulation are analyzed. For instance, it is found that after the major Baltic inflow in January 2003 saline water passing the Słupsk Furrow flows directly towards northeast along the eastern slope of the Hoburg Channel. However, after the baroclinic summer inflow in August/September 2002 the deep water flow spreads along the southwestern slope of the Gdansk Basin. Further, the model results show that the patterns of mean vertical advective fluxes across the halocline that close the large-scale vertical circulation are rather patchy. Mainly within distinct areas are particles of the saline inflow water advected vertically from the deep water into the surface layer. To analyze the time scales of the circulation mean ages of various water masses are calculated. It is found that at the sea surface of the Bornholm Basin, Gotland Basin, Bothnian Sea, and Bothnian Bay the mean ages associated to inflowing water from Kattegat amount to 26–30, 28–34, 34–38, and 38–42 years, respectively. Largest mean sea surface ages of more than 30 years associated to the freshwater of the rivers are found in the central Gotland Basin and Belt Sea. At the bottom the mean ages are largest in the western Gotland Basin and amount to more than 36 years. In the Baltic proper vertical gradients of ages associated to the freshwater inflow are smaller than in the case of inflowing saltwater from Kattegat indicating an efficient recirculation of freshwater in the Baltic Sea.     

Age and growth rates of ferromanganese concretions from the gulf of Finland derived from 210Pb measurements

The formation of ferromanganese concretions on continental shelves is a widespread recent biogeochemical process, which is particularly intense in the Baltic Sea. The proposed new technique for dating ferromanganese concretions is based on the equilibrium ²¹⁰Pb, which is produced immediately within them due to the decay of ²²⁶Ra, which is intensely sorbed by concretions from the seawater. This method is principally different from the traditional dating of bottom sediments using nonequilibrium ²¹⁰Pb, which represents a decay product of atmospheric Ra. A mathematical tool for the calculation of the concretion ages is proposed. The latter is used for calculating the ages and growth rates of ferromanganese concretions belonging to two morphological varieties. The age and average growth rates of spheroidal concretions are estimated to be 670–850 years and 0.014 mm/year, respectively. The central part of a pancake-shaped concretion is dated back to 2500–3800 years, and its calculated respective horizontal and vertical growth rates are approximately 0.028 and 0.004 mm/year.     

Causes of different impact of Major Baltic Inflows on cod reproduction in the Gotland Basin of the Baltic Sea

The impact of the Major Baltic Inflows (MBIs) of 1976, 1993, and 2003 on cod reproduction in the Gotland Basin of the Baltic Sea is considered based on calculations of the eastern Baltic cod egg abundance and offspring survival indices. The reproductive success (1976–1977) was defined by the elevation of the 11 psu isohaline and deepening of the 2 mL/L isooxygene surface, which provided the formation of a water layer suitable for cod spawning at a depth of 90–130 m. Prerequisites of the appearance of the reproductive layer in 1976–1977 were a previously high salinity level and penetrating two successive MBIs in one year. The cause of the weak MBI impact in 1993 was the previous salinity minimum; in 2003 it was rapid oxygen depletion due to an increase in temperature. As a result of their weaker influence, small and fragmented cod spawning biotopes appeared in the Gotland Basin.     

Uptake of selenium and other oxyanionic elements in marine ferromanganese concretions of different origins

The concentration of selenium in marine ferromanganese concretions varies between 0.02 and 1.2 mg kg⁻¹, with an average of 0.6 mg kg⁻¹. This is about two orders of magnitude lower than previously reported. In contrast to minor cationic elements, the concentrations of selenium are relatively uniform between ferromanganese concretions of different origins, except for hydrothermal crusts. It shows the same trends of element enrichment as other oxyanionic elements. The incorporation of selenium into ferromanganese concretions is attributed to adsorption of selenate on iron and manganese oxides.     

Synoptic variability of the currents in the Gotland Basin of the Baltic Sea

The series of long-term observations of synoptic-scale currents obtained by instrumental measurements at the moorings in the Gotland Basin of the Baltic Sea are analyzed. The results of the statistical analysis of the currents reveal their wave structure. The characteristics of the low-frequency waves received on the basis of the cross-spectral analysis show that, in the range of periods from 2 to 20 days, they propagated in the southwestern, southeastern, and northwestern directions with phase speeds of 0.02–2.08 m/s and have lengths from 28 to 431 km. It is suggested that the distinguished wavelike perturbations of the synoptic-scale currents are related to topographic waves. The analysis of the meteorological conditions and the results of the numerical hydrodynamic modeling of the Baltic Sea free low-frequency fluctuations led us to conclude that the most possible mechanism of the generation of the intense wave-like oscillations of synoptic-scale currents in the Gotland Basin is the resonance between the anemobaric forces and the relatively slow-moving anticyclones over the open Baltic Sea and the eigenmode of the basin.     

Dissolved uranium in the Baltic Sea

Filtered water from the Baltic Sea was analysed for uranium concentration and ²³⁴U/²³⁸U activity ratio with alpha-ray spectrometry. The uranium concentration shows a strong correlation to salinity, the correlation coefficient being close to 0.98. Consequently, the uranium concentration increases from 0.15 μg kg⁻¹ in the northern part, dominated by fresh water, to above 1.0 μg kg⁻¹ in the Belt Sea. However, the data also show that dissolved uranium is not strictly conservative in the Baltic. In deeper intermittently anoxic basins of the Baltic Proper, the element is removed from the water phase and incorporated into the sediment. This is most evident in the Gotland Deep, which has been anoxic below 200 m depth since 1979.     

Oceanological Research in the Baltic Sea during the 56th Cruise of the Passenger Vessel Akademik Ioffe

Oceanology - During the 56th cruise of the P/V Akademik Ioffe (August 2020) in the Baltic Sea, hypoxia was registered at a water depth of 80 m, hydrogen sulfide in the East Gotland Basin was...     

Rare earth elements and yttrium in ferromanganese deposits from the South China Sea: distribution, composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements(REE) and yttrium(REY),with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10~(–6) to 2 919.4×10~(–6),with an average value of 1 459.5×10~(–6).Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE(LREE) and heavy REE(HREE) oxides of the ferromanganese deposits in the study area can be classified into four grades: non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.     

Photobleaching of fluorescence and the organic carbon concentration in a coastal environment

In order to investigate the photobleaching potential of estuarine waters from different depths and redox conditions and with varying degree of biological activity, filtered, unfiltered and chloroform-poisoned water samples from the Baltic Sea were exposed to ambient sunlight. Fluorescence, at excitation 350 nm and emission 450 nm, was used as an indication of humic substance concentration. Fluorescence and organic carbon concentration were measured at regular time intervals during light exposure. We found that the decrease in humic substance fluorescence can be fitted to an exponential decay function. The fluorescence half-lives were within the range 0.4 – 4.6 days in different water masses, with fluorescence decreasing to between 20% and 60% of initial concentration, respectively. Results from the curve fitting procedure indicate a rest concentration of humic substance fluorescence, similar among the sampled sites, that is resistant to further photochemical degradation. The largest relative decreases in fluorescence were found in deep waters, but samples from deep waters also had a higher fluorescence rest concentration than samples from surface waters. Biological activity was reduced by filtering the samples through 0.2μm pore size filters or adding chloroform. No statistically significant differences were found after 3 days of irradiation between samples with and without treatment to reduce biological activity. The highest initial fluorescence values and the largest fluorescence decrease were found in the anoxic waters of the Gotland Deep. The organic carbon concentrations decreased 3–7% at all stations. The shortest half-life of humic substance, and the largest decrease in organic carbon concentrations, were found in samples from the northern basins of the Baltic Sea.     

Methane fluxes in the southeastern Baltic Sea

New data from surveys of gas-bearing mud areas in the Gdansk Deep (southeastern Baltic Sea) were collected during four research cruises in 2009–2011. These revealed the presence of seven large pockmarks apart from the three already known, and enabled significant improvement of the existing digital map of gassy mud distribution. Based on geochemical sediment analyses, calculated diffusive methane fluxes from the upper (0–5?cm) seabed layer into near-bottom waters were highest—3.3?mmol/(m²?day)—in pockmark mud, contrasting strongly with the minimum value of 0.004?mmol/(m²?day) observed in typical, background mud. However, fluxes of less than 0.1?mmol/(m²?day) were observed in all sediment types, including pockmarks. In a newer attempt to roughly estimate budgets at a more regional scale, diffusive methane venting amounts to 280?×?10⁶?mmol/day for southeastern Baltic Sea muddy sediments. Elongated pockforms in the southern Gotland Deep, known since the end of the 1980s as pockmarks, had methane concentrations that were similar to those of gassy mud from the Gdansk Basin, and there was no geo-acoustic evidence of considerably increased gas levels.     

Variations in the elemental composition of ferromanganese structures from Lake Baikal

The elemental composition of ferromanganese sedimentary structures from the bottom of Lake Baikal represented by nodules and crusts, as well as the enclosing sediments, have been studied by the atomic absorption, chemical, and ICP-MS methods. It is established that the contents of the rock-forming and accompanying elements in them are highly variable. In this connection, the examined samples are divided in two groups differing by their Mn/Fe values. In most of the samples, they range from 0.01 to 0.1, although some of the ferromanganese structures or their parts are substantially enriched in manganese. The contents of most of the rare and dispersed elements in the ferromanganese structures are usually at the background level, although the samples maximally enriched in iron or manganese are characterized by relatively high copper, nickel, cobalt, vanadium, zinc, and molybdenum concentrations.     

Element composition of ferromanganese concretions in the Black Sea

The ferromanganese concretions spread at the bottom of the shallow northwestern part of the Black Sea are mainly represented by Fe and Mn hydrate nodules on shells and substituted worm tubes. The element composition of these formations was found by the methods of chemical, atomic-absorbtion, neutron activation, and plasmic (ICP-MS) analyses. It is established that the content and the ratio of Fe and Mn in the concretions ranges within considerable limits, which controls the occurrence of several associated iron-free metals and microelements, some which have not been previously studied in the Black Sea concretions.     

Composition of ferromanganese nodules from Riga Bay (Baltic Sea)

An average sample of ferromanganese nodules from Riga Bay was investigated by analytical electron microscopy coupled with atomic absorption, neutron activation, and ICP-MS methods. It is established that the nodules consist of colloform and poorly crystallized Fe and Mn hydroxides with an admixture of dispersed inclusions of better crystallized particles allowing revealing their mineralogical nature by the microdiffraction method. The major mineral phases are ferroxigite and Fe-vernadite with subordinate magnetite, asbolane, and todorokite. The chemical composition of the nodules is dominated by iron followed by cobalt and lead, while nickel, molybdenum, and tungsten associate with the manganese phase. The concentration of several minor elements in the Riga Bay nodules is slightly lower as compared with their average values for the entire Baltic Sea; some elements such as silver, bismuth, cadmium, niobium, tin, and thallium were never analyzed before.     

The effect of manganese oxide scavenging on molybdenum in saanich inlet,British Columbia

A simple colorimetric method was developed for determining molybdenum in seawater by solvent extraction of its dithiolate and was then applied during a nine month study of Saanich Inlet. This inlet is a fjord on the coast of Vancouver Island, British Columbia, in which the bottom waters alternate between a weakly oxygenated and anoxic state. Results are given for the concentrations of dissolved and suspended molybdenum, suspended manganese, dissolved oxygen and of salinity measurements. Salinity-molybdenum correlations demonstrate that the deep waters are deficient in molybdenum, a conclusion consistent with reports that the sediments deposited in the reducing zone are enriched with molybdenum precipitated from the anoxic bottom waters. Suspended manganese, which occurs in large amounts as a result of the oxidative precipitation of dissolved Mn(II) diffusing from anoxic waters, has a distribution that is directly correlated to that of suspended molybdenum and which tends to be inversely related to that of dissolved molybdenum, suggesting that molybdenum is being coprecipitated with manganese oxides. Such a hypothesis is supported by the fact that the average molybdenum to manganese weight ratio of suspended matter closely approximates that of local manganese nodules, and by a mathematical analysis of the distribution data which includes development of a model for scavenging. Computations using the model relationships indicate that manganese oxide scavenging tends to concentrate molybdenum in the reducing waters where the anoxic processes responsible for its deposition in the sediments become operative. Additional calculations based upon current estimates of oceanic residence times suggest that manganese-oxide scavenging operating on an oceanic scale could be removing approximately 10% of the molybdenum being added to the oceans.     

中国海域固体矿产资源分布及其区划——砂矿资源和铁锰(微)结核-结壳

综述和研究了我国海域砂矿资源和(微)结核—结壳的分布及其区划。我国的滨海砂矿广泛分布于渤海、黄海、东海和南海,但各省区的砂矿资源分布不同。近年来在我国海域新发现和圈定了多处砂矿品位异常区和矿物高含量区,可分为3个成矿带和24个成矿远景区,资源储量可观。在黄海、东海仅分布铁锰结核,没有发现铁锰结壳,但它们的金属元素含量低,没有潜在资源意义。南海东北陆坡、中央海盆西部和中部是(微)结核、结壳分布较多的区域。南海东北陆坡、海山及其周缘坡脚处的(微)结核、结壳其稀土元素含量较高,可能具有一定的潜在经济价值,今后调查中应引起重视。     

The key features of the bottom sediment composition in the anoxic Lake Mogil’noe

In the summer 2006, integrated geological, geochemical, hydrological, and hydrochemical studies were performed on the relict anoxic Lake Mogil’noe (down to 16 m depths) located on Kil’din Island in the Barents Sea. The chemical and grain-size composition of the bottom sediments were compared for the lake (a permanently anoxic basin) and the Baltic Sea Deeps (periodically anoxic basins). The vertical location of the hydrogen sulfide layer boundary in the lake (9–11 m depths) was practically the same from 1974 up to now. The concentrations of suspended particulate matter in the lake in June and July 2006 appeared to be close to its summer concentrations in the seawaters of the open part of the Baltic Sea. The mud from Lake Mogil’noe compared to those of the Baltic Sea Deeps are characterized by fluid and flake consistency and by pronounced admixtures of sandy and silty fractions probably of eolic origin. The lacustrine mud contain much plant remains; iron sulfides and vivanite were also found in ooze. The concentrations of 22 elements determined in the lacustrine bottom sediments were of the same levels as those found here 33 years ago. The concentrations also appeared to be close to those in the corresponding grain-size types of the bottom sediments in the Baltic Sea. The low C_org/N value (5% on average) in the mud of Mogil’noe Lake compared to the values for the mud of the Baltic Sea Deeps (10% on average) points to the considerable planktogenic component in the organic matter composition of the lacustrine mud. No indications were reveled for anthropogenic contaminations of the lacustrine bottom sediments with toxic metals.     

Suboxic and Anoxic Conditions of Deep Waters in the Gdansk Basin of the Baltic Sea

Oceanology - Long-term variability of the concentrations of oxygen and hydrogen sulfide in deep waters of the Gdansk Basin of the Baltic Sea for the last 25 years was considered. The dependence of...     

One hundred years of hydrographic measurements in the Baltic Sea

The first measurements of salinity of the deep water in the open Baltic Sea were made in the last decades of the 1800s. At a Scandinavian science meeting in Copenhagen in 1892, Professor Otto Pettersson from Sweden suggested that regular measurements of hydrographic parameters should be carried out at some important deep stations in the Baltic Sea. His suggestion was adopted and since that time we have rather complete hydrographical data from the Bornholm Deep, the Gotland Deep, and the Landsort Deep and from some stations in the Gulf of Bothnia. The measurements were interrupted in the Baltic Proper during the two World Wars. At the beginning only salinity, temperature and dissolved oxygen were measured and one or two expeditions were carried out annually, mostly in summer. In the 1920s also alkalinity and pH were occasionally measured and total carbonate was calculated. A few nutrient measurements were also carried out. After World War II we find results from four or more expeditions every year and intercalibration of methods was arranged. Results of temperature, salinity and dissolved oxygen measurements from the Bornholm Deep, the Gotland Deep, the Landsort Deep and salinity measurements from three stations in the Gulf of Bothnia, covering the whole 20th century are presented and discussed. The salinity distribution and the variations between oxygen and hydrogen sulphide periods in the deep water of the Gotland Deep and the Landsort Deep are demonstrated. Series of phosphate and nitrate distribution in the Gotland Deep are shown from the 1950s to the present and the effects of the stagnant conditions are briefly discussed. Two large inflows of highly saline water, the first during the First World War and the second in 1951, are demonstrated. The 20th century minimum salinity of the bottom water in the Baltic Proper in 1992 is discussed.