Concentrations of suspended matter and heavy metals in melted ice- and snow water from the Barents Sea

In September-October 1998, during Cruise 14 of R/V Akademik Fedorov to the Barents Sea, in the region of 82° N between the Spitsbergen and Novaya Zemlya archipelagos samples of snow and ice were collected within four polygons. By means of atomic absorption with an electothermal atomizer (onboard the ship) in filtered (dissolved form) and unfiltered (sum of dissolved and particulate forms) samples of snow melt and ice melt concentrations of Fe, Mn, Cu, Cr, Ni, Co, Pb, and Cd were determined in order to estimate level of potential contamination of snow and ice with these metals. Excluding data on Ni, Cd (and probably Cu) in ice that were regarded to be unsatisfactory because of probable contamination of the ice samples during drilling concentrations of all the elements in snow and ice of the northern part of the Barents Sea appeared to be close to their background values or below. An attempt to identify the main sources of metal supply to snow from the atmosphere by comparison of ratios of metal particulate form to total content in snow of the Barents Sea and the same ratios in snow samples from clean regions of Finland and from contaminated areas of the Kola Peninsula showed that aerosols in the area of the expedition were supplied into the Barents Sea atmosphere from different sources, both natural and anthropogenic.

Atmospheric and seawater carbon dioxide at time series station DYFAMED

A time series of fCO2, SST, and fluorescence data was collected between 1995 and 1997 by a CARIOCA buoy moored at the DyFAMed station (Dynamique des Flux Atmospheriques en Mediterranée) located in the northwestern Mediterranean Sea. On seasonal timescales, the spring phytoplankton bloom decreases the surface water fCO2 to approximately 290 µatm, followed by summer heating and a strong increase in fCO2 to a maximum of approximately 510 µatm. While the DELTA fCO2 shows strong variations on seasonal timescales, the annual average air-sea disequilibrium is only 2 µatm. Temperature-normalized fCO2 shows a continued decrease in dissolved CO2 throughout the summer and fall at a rate of approximately 0.6 µatm/d. The calculated annual air-sea CO2 transfer rate is -0.10 to -0.15 moles CO2 m-2 y-1, with these low values reflecting the relatively weak wind speed regime and small annual air-sea fCO2 disequilibrium. Extrapolating this rate over the whole Mediterranean Sea would lead to a flux of approximately -3 * 10**12 to -4.5 * 10**12 grams C/y, in good agreement with other estimates. An analysis of the effects of sampling frequency on annual air-sea CO2 flux estimates showed that monthly sampling is adequate to resolve the annual CO2 flux to within approximately ±10 - 18% at this site. Annual flux estimates made using temperature-derived fCO2 based on the measured fCO2-SST correlations are in agreement with measurement-based calculations to within ± 7-10% (depending on the gas transfer parameterization used), and suggest that annual CO2 flux estimates may be reasonably well predicted in this region from satellite or model-derived SST and wind speed information.

Investigations on sediments from Lake Nam Co (Tibetan Plateau)

This study focuses on the analysis of lake sediments retrieved from the deepest part of Lake Nam Co (Tibetan Plateau). One gravity core of 115 cm length, covering the last ~ 4000 cal BP, was analyzed for geochemical and biological parameters. High organic content at ~ 4000 cal BP and the coinciding presence of pyrite framboids until ~ 2000 cal BP point to hampered decomposition of organic material due to anoxic conditions within the lake sediments. At the same time sedimentological and biological proxies suggest a rather high lake level, but still ~ 5 m below the recent one, with less saline lake water due to enhanced monsoonal activity. During this time a change in the source of organic matter to lowered input of terrestrial components is observed. A rather quick shift to a dry environment with less monsoonal influence and a lake level ~ 15 m lower than today at ~ 2000 cal BP lead to the oxygenation of sediment, the degradation of organic matter and the absence of pyrite. Oscillations of the lake level thereafter were of minor amplitude and not able to establish anoxia at the lake bottom again. A wet spell between ~ 1500 cal BP and ~ 1150 cal BP is visible in proxies referring to catchment hydrology and the ostracod-based water depth transfer function gives only a slightly elevated lake level. The last ~ 300 years are characterized by low TOC and rising TN values reflecting enhanced nutrient supply and hence an advancing influence of human activity in the catchment. Decreasing TOC/TN values point to a complete shift to almost solely aquatic biomass production. These results show that hydrological variations in terms of lake level change based on monsoonal strength can be linked to redox conditions at the lake bottom of Nam Co. Comparison with other archives over larger parts of the Tibetan Plateau and beyond exhibits a rather homogeneous climatic pattern throughout the late Holocene.

Contents of major and noble chemical elements in phosphorites and bottom sediments

Ag and Au are typically concentrated in phosphorites; they genetically related to organic matter of bottom sediments that extract these elements from seawater or interstitial water. Consequently, the phosphorites inherit Ag and Au from host sediments that are not always enriched in them. In contrast to other organic-rich sediments, analyzed sample of recent diatom ooze from the Namibian shelf is not enriched in Ag and Au, although some sediments from this region are enriched in Au. In addition to authigenic Au, allochthonous Au associated with quartz grains and micrograins can also be present in shelf phosphorites. This was observed in oceanic phosphorites of various types. Anomalous Au and Fe contents recorded in one seamount phosphorite sample can be related to extraction of Au and nonferrous metals by ferromanganese hydroxides from seawater. This process can serve as one of major mechanisms of Au supply to ferromanganese crusts on seamounts. Phosphorites and sediments are enriched in Ru simultaneously with U. Author's data show that U content varies from 17 (seamount phosphorite) to 887 ppm (Pleistocene phosphorite nodule from the Namibian shelf). This is probably caused by different types of behavior of light and heavy PGEs in the marine environment.

Carbon and Lead chemistry of sediments from the Middle Atlantic Bight

A mass budget was constructed for organic carbon on the upper slope of the Middle Atlantic Bight, a region thought to serve as a depocenter for fine-grained material exported from the adjacent shelf. Various components of the budget are internally consistent, and observed differences can be attributed to natural spatial variability or to the different time scales over which measurements were made. The flux of organic carbon to the sediments in the core of the depocenter zone, at a water depth of 1000 m, was measured with sediment traps to be 65 mg C m**-2 day**-1, of which 6-24 mg C m**-2 day**-1 is buried. Oxygen fluxes into the sediments, measured with incubation chambers attached to a free vehicle lander, correspond to total carbon remineralization rates of 49-70 mg C m**-2 day**-1. Carbon remineralization rates estimated from gradients of Corg within the mixed layer, and from gradients of dissolved ammonia and phosphate in pore waters, sum to only 4-6 mg C m**-2 day**-1. Most of the Corg remineralization in slope sediments is mediated by bacteria and takes place within a few mm of the sediment-water interface. Most of the Corg deposited on the upper slope sediments is supplied by lateral transport from other regions, but even if all of this material were derived from the adjacent shelf, it represents <2% of the mean annual shelf productivity. This value is further lowered by recognizing that as much as half of the Corg deposited on the slope is refractory, having originated by reworking from older deposits. Refractory Corg arrives at the sea bed with an average 14C age 600-900 years older than the pre-bomb 14C age of DIC in seawater, and has a mean life in the sediments with respect to biological remineralization of at least 1000 years. Labile carbon supplied to the slope, on the other hand, is rapidly and (virtually) completely remineralized, with a mean life of < 1 year. Carbon-14 ages of fine-grained carbonate and organic carbon present within the interstices of shelf sands are consistent with this material acting as a source for the old carbon supplied to the slope. Winnowing and export of reworked carbon may contribute to the often-described relationship between organic carbon preservation and accumulation rate of marine sediments.

Nd and Pb isotope signatures of the clay-size fraction of sediment core MD99-2227

Nd and Pb isotopes were measured on the fine fraction of one sediment core drilled off southern Greenland. This work aims to reconstruct the evolution of deep circulation patterns in the North Atlantic during the Holocene on the basis of sediment supply variations. For the last 12 kyr, three sources have contributed to the sediment mixture: the North American Shield, the Pan-African and Variscan crusts, and the Mid-Atlantic Ridge. Clay isotope signatures indicate two mixtures of sediment sources. The first mixture (12.2-6.5 ka) is composed of material derived from the North American shield and from a "young" crustal source. From 6.5 ka onward the mixture is characterized by a young crustal component and by a volcanic component characteristic of the Mid-Atlantic Ridge. Since the significant decrease in proximal deglacial supplies, the evolution of the relative contributions of the sediment sources suggests major changes in the relative contributions of the deep water masses carried by the Western Boundary Undercurrent over the past 8.4 kyr. The progressive intensification of the Western Boundary Undercurrent was initially associated mainly with the transport of the Northeast Atlantic Deep Water mass until 6.5 ka and with the Denmark Strait Overflow Water thereafter. The establishment of the modern circulation at 3 ka suggests a reduced influence of the Denmark Strait Overflow Water, synchronous with the full appearance of the Labrador Seawater mass. Our isotopic data set emphasizes several changes in the relative contribution of the two major components of North Atlantic Deep Water throughout the Holocene.

Sedimentology and Lead and Strontium isotope ratios of Miocene sediments from the Kerguelen Plateau

Characterization of sediment from Ocean Drilling Program Site 745, representing the East Kerguelen Ridge sediment drift, addresses important issues surrounding the timing of Miocene to present East Antarctic ice sheet stability and oceanic environmental change. Our results show three periods of greatly enhanced accumulation of Antarctic-derived sediment, at 6.4-5.9 Ma, 4.9-4.4 Ma and 1.1-0.8 Ma, potentially indicative of warmer, less stable ice sheets at these times. Conversely, the accumulation of Antarctic-derived material is comparatively less during the middle of the Pliocene warm epoch (4.8-3.2 Ma). The deep flow forming the Kerguelen drift was stronger during the latest Miocene and earliest Pliocene and has decreased in intensity continuously since then.

Gotland Deep (Baltic Sea) independent age model based on Palaeomagnetic Secular Variation (PSV) and lead (Pb) deposition profiles

Dating of sediment cores from the Baltic Sea has proven to be difficult due to uncertainties surrounding the 14C reservoir age and a scarcity of macrofossils suitable for dating. Here we present the results of multiple dating methods carried out on cores in the Gotland Deep area of the Baltic Sea. Particular emphasis is placed on the Littorina stage (8 ka ago to the present) of the Baltic Sea and possible changes in the 14C reservoir age of our dated samples. Three geochronological methods are used. Firstly, palaeomagnetic secular variations (PSV) are reconstructed, whereby ages are transferred to PSV features through comparison with varved lake sediment based PSV records. Secondly, lead (Pb) content and stable isotope analysis are used to identify past peaks in anthropogenic atmospheric Pb pollution. Lastly, 14C determinations were carried out on benthic foraminifera (Elphidium spec.) samples from the brackish Littorina stage of the Baltic Sea. Determinations carried out on smaller samples (as low as 4 µg C) employed an experimental, state-of-the-art method involving the direct measurement of CO2 from samples by a gas ion source without the need for a graphitisation step - the first time this method has been performed on foraminifera in an applied study. The PSV chronology, based on the uppermost Littorina stage sediments, produced ten age constraints between 6.29 and 1.29 cal ka BP, and the Pb depositional analysis produced two age constraints associated with the Medieval pollution peak. Analysis of PSV data shows that adequate directional data can be derived from both the present Littorina saline phase muds and Baltic Ice Lake stage varved glacial sediments. Ferrimagnetic iron sulphides, most likely authigenic greigite (Fe3S4), present in the intermediate Ancylus Lake freshwater stage sediments acquire a gyroremanent magnetisation during static alternating field (AF) demagnetisation, preventing the identification of a primary natural remanent magnetisation for these sediments. An inferred marine reservoir age offset (deltaR) is calculated by comparing the foraminifera 14C determinations to a PSV & Pb age model. This deltaR is found to trend towards younger values upwards in the core, possibly due to a gradual change in hydrographic conditions brought about by a reduction in marine water exchange from the open sea due to continued isostatic rebound.

Cadmium and lead in sea ice and seawater of the Amur Bay, Sea of Japan

Distribution of Cd and Pb in sea ice and in under-ice water of the Amur Bay at the end of February 1998 is considered. The metals were determined by technique of inversion voltammetry. Contribution of Cd and Pb from atmospheric precipitation and from under-ice water to sea ice examined is discussed. On the basis of analysis of vertical distribution in ice, atmospheric fluxes supplying metals to the aquatic area of the bay are estimated at 100 and 2000 µg/m**2/year for Cd and Pb, respectively. Concentrations of Cd and Pb found in middle and lower parts of ice cores allow to suggest that their accumulation relative to main ions of seawater occurs in the ice. Estimated enrichment factors of Cd and Pb in sea ice relative to seawate are ~9 and ~5. A possible mechanism of relative metal accumulation in sea ice is considered.

Lead and strontium isotopic composition of some metalliferous and pelagic sediments and basalts at DSDP Leg 70 Holes

In recent years, metalliferous sediments have been discovered overlying newly generated oceanic crust in the East Pacific, North Atlantic, Indian Ocean, Red Sea, Gulf of Aden, and elsewhere (e.g., Boström, 1973; Lalou et al., 1977; Bischoff, 1969; Boström and Fisher, 1971; Cann et al., 1977, respectively). Such material has also been recovered by drilling from sediments lying upon older oceanic crust (Boström et al., 1972, 1976; Horowitz and Cronan, 1976). Hydrothermal circulation of seawater at a spreading ridge results in the leaching of Fe, Mn, and possibly other elements from the basaltic volcanic layer and their transport and discharge into ocean bottom waters, whereupon fine-grained Fe-Mn-rich precipitates form and settle into the ambient sediment (cf. Corliss, 1971; Dasch et al., 1971; Spooner and Fyfe, 1973; Bischoff and Dickson, 1975; Heath and Dymond, 1977; Corliss et al., 1979, Edmond et al., 1979). Mn-rich crusts have also been recovered from active ridges and are inferred to have formed in the vicinity of hydrothermal discharge areas (Scott et al., 1974; Moore and Vogt, 1976; Corliss et al., 1978; Hoffert et al., 1978). The source of the trace elements in the metalliferous deposits is generally not clear. They may be derived from seawater by adsorption onto the precipitates or crusts, or from hydrothermal solutions which have leached them from the basalts. Pb, however, can be used as a geochemical tracer because of the known isotopic compositional differences between oceanic basalts and seawater. Isotopic investigations of Pb in ferruginous sediments from the East Pacific have shown that it has been derived partly or mostly from a basaltic source (Bender et al., 1971; Dasch et al., 1971; Dymond et al., 1973). In the present study, Pb isotopic analyses have been made of a suite of metalliferous sediments (nontronite, Mn-oxide crust, Mn-Fe-oxide mud), pelagic sediments, and basalts from the Galapagos mounds area. The main purposes of the Pb study were to determine the source or sources of Pb in the metalliferous sediments, and whether or not stratigraphic variations exist in the isòtopic composition of Pb in the sediments.