(Table 1) Grain size composition and heavy metal speciations in bottom sediments of the Ussuri Bay, Sea of Japan

Changes in concentration levels and speciation of heavy metals during sedimentation on example of a typical semi-closed bay, where bottom sediments have formed due to river run-off, are under consideration. It is shown that due to desorption of mobile manganese, zinc and copper entered the bay with river suspended matter, their total contents in bottom sediments decrease and percentages of lithogenic forms increase. Contents and speciation of iron in bottom sediments are determined by its participation in coagulation of river colloids in the mixing zone and by mechanical differentiation of sedimentary material.

Tissue metal concentrations and metal transfer functions of Glaucous Gulls (Larus hyperboreus) from Bjørnøya and Jan Mayen

Heavy metals (Cd, Cu, Fe, Mn and Zn) concentrations were determined in different tissues (muscle, kidney, liver, brain, gonads, heart and feathers) of Glaucous Gulls (Larus hyperboreus) from Bjornoya and Jan Mayen. The age and spatial dependent variations in heavy metals were quantified and interpreted in view of the three chemometric techniques, i.e. non-parametric Mann-Whitney U test, redundancy gradient analysis and detrended correspondence analysis. The Glaucous Gulls from Bjornoya contained significantly higher (p < 0.05) levels of Cd, Cu and Zn than those inhabited Jan Mayen. Adult birds were characterized by greater (p < 0.01) concentration of muscle, hepatic and renal heavy metals in comparison to chicks. Insignificantly higher slope constant Zn/Cd for the liver than for the kidney may reflect insignificant Cd exposure. Estimate of transfer factor (TF) allows us to assess variations in heavy metal concentrations during the individual development of Glaucous Gulls. It may be stated that there is a distinct increase of bioaccumulation of all the studied metals during subsequent stages of the bird life.

(Table 1) Composition of manganese-iron accumulates in the Kiel Bay, western Baltic Sea

Manganese-iron accumulates in the Kiel Bay were investigated with regard to their occurence, chemical composition and formation. Three morphologically different types were identified: a) growth on mussels, b) spherical nodules (ca. 1-3 cm) and c) disshaped symetrical and asymetrical nodules (up to 10 cm). Average values from 110 accumulates representing the three types were: Mn 29.3%, Fe 10.0%, Co 77 ppm, Ni 97 ppm, Cu 21 ppm and Zn 340 ppm. Accumulates on mussels showed the highest trace metal concentrations. A growth rate of ca. 0.6 mm/yr for type (a) was estimated. Heavy metal concentrations were determined in ca. 60 sediment and 30 pore water samples, and in 110 Baltic sea water samples. During certain periods, large increases in Mn values (up to 400 (µg/l) were found in the deeper waters. These concentrations develop during periods of strong stagnant conditions in the sediments where dissolution of Mn oxides, and diffusion mobilizes the Mn into the overlying waters. The manganese is then reprecipitated close to the boundary of the O2-enriched surface waters. This critical O2-concentration was found to be 40% saturation. In the Kiel Bay, Mn-Fe-accumulates are found in a zone which marks the upper limit sometimes reached by the deep waters of lower O2-concentration. Additionally, the availability of larger particles (especially stones or mussels) on the sediment surface is necessary. These conditions are met in the Kiel Bay in a water depth of 20-28 m at several places.

Heavy metals and carbon isotope concentrations in recent Baltic Sea sediments

Recent sediment cores of the western Baltic Sea were analyzed for heavy metal and carbon isotope contents. The sedimentation rate was determined from radiocarbon dates to be 1.4 mm/yr. The 'recent age' of the sediment was about 850 yr. Within the upper 20 cm of sediment, certain heavy metals became increasingly enriched towards the surface; Cd, Pb, Zn and Cu increased 7-, 4-, 3- and 2-fold, respectively, whereas Fe, Mn, Ni and Co remained unchanged. Simultaneously, the radiocarbon content decreased by about 14 per cent. The enrichment in heavy metals as well as the decrease in the 14C-concentration during the last 130 ± 30yr parallels industrial growth as reflected in European fossil fuel consumption within that same period of time. The near-surface sediments are affected by residues released from fossil fuels at the rate of about 30 g/m**2 yr for the past two decades. The residues have a pronounced effect on the heavy metal and carbon isotope composition of the most Recent sediments allowing estimates to be made for sedimentation, erosion and heavy metal pollution.

(Table 2) Concentration of heavy metals and organic carbon, and 210Pb activity of sediments near Büsum, eastern Wadden Sea

A 3.38 m long sediment core raised from the tidal flat sediments of the 'Blauortsand' in the Wadden Sea northwest of Büsum (Schleswig-Holstein, Germany) was analysed in order to investigate long term changes in sediment pollution with Pb, Cu, Zn and Cd. Comparison with the topographic maps since 1952 and 210Pb activity allowed a general dating of the sediment succession in the core. The heavy metal concentrations including 210Pb of the < 20 µm grain-size fraction in thick sediment slices below 1.30 m indicated background niveaus. Their values increased and reached modern levels in the upper sediment layers of the core above 1 m. The increments for Pb, Cu, Zn was 1 to 3 fold and Cd up to 11 fold since the second half of the 19th century. More investigations are needed to quantify the geographical extent and history of the contaminations shown in this pilot study.

Contents of metal cations exchange capacity of ore minerals in ferromanganese micronodules from the Atlantic, Indian and Pacific Oceans

Results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules from diverse bioproductive zones of the World Ocean were considered. It was found that sorption behavior of these minerals was similar to that of ore minerals from ferromanganese nodules and low-temperature hydrothermal crusts. The exchange complex of minerals in the micronodules includes the major (Na**+, K**+, Ca**2+, Mg**2+, and Mn**2+) and subordinate (Ni**2+, Cu**2+, Co**2+, Pb**2+, and others) cations. Reactivity of theses cations increases from Pb**2+ and Co**2+ to Na**+ and Ca**2+. Exchange capacity of micronodule minerals increases from alkali to heavy metal cations. Capacity of iron and manganese minerals in oceanic micronodules increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite ~= Fe-vernadite + Mn-feroxyhyte. Obtained data supplement available information on ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in redistribution of metal cations at the bottom water - sediment interface during micronodule formation and growth.

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.