Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

Sediment and pore water chemistry of cores 214 and 755 recovered during Meteor M72/1 and POSEIDON cruise POS317/2, northwestern Black Sea

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (SO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate-methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events for which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, 'relict' barite fronts would only be preserved for a few thousands of years, if at all.

Chlorofluorocarbons, helium, and neon measured on water bottle samples during POLARSTERN cruise ANT-XXII/2 (ISPOL)

During Ice Station POLarstern (ISPOL; R.V. Polarstern cruise ANT XXII/2, November 2004-January 2005), hydrographic and tracer observations were obtained in the western Weddell Sea while drifting closely in front of the Larsen Ice Shelf. These observations indicate recently formed Weddell Sea Bottom Water, which contains significant contributions of glacial melt water in its upper part, and High-Salinity Shelf Water in its lower layer. The formation of this bottom water cannot be related to the known sources in the south, the Filchner-Ronne Ice Shelf. We show that this bottom water is formed in the western Weddell Sea, most likely in interaction with the Larsen C Ice Shelf. By applying an Optimum Multiparameter Analysis (OMP) using temperature, salinity, and noble gas observations (helium isotopes and neon), we obtained mean glacial melt-water fractions of about 0.1% in the bottom water. On sections across the Weddell Gyre farther north, melt-water fractions are still on the order of 0.04%. Using chlorofluorocarbons (CFCs) as age tracers, we deduced a mean transit time between the western source and the bottom water found on the slope toward the north (9±3 years). This transit time is larger and the inferred transport rate is small in comparison to previous findings. But accounting for a loss of the initially formed bottom water volume due to mixing and renewal of Weddell Sea Deep Water, a formation rate of 1.1±0.5 Sv in the western Weddell Sea is plausible. This implies a basal melt rate of 35±19 Gt/year or 0.35±0.19 m/year at the Larsen Ice Shelf. This bottom water is shallow enough that it could leave the Weddell Basin through the gaps in the South Scotia Ridge to supply Antarctic Bottom Water. These findings emphasize the role of the western Weddell Sea in deep- and bottom-water formation, particularly in view of changing environmental conditions due to climate variability, which might induce enhanced melting or even decay of ice shelves.

(Table 1) Boron concentration and d11B values of interstitial water from IODP Holes 308-U1319A, U1320A, U1322B and U1324B

The Integrated Ocean Drilling Program Expedition 308 (IODP308) drilled normal-pressured sediments from the Brazos-Trinity Basin IV and over-pressured sediments from the Ursa Basin on the northern slope of the Gulf of Mexico. The interstitial water samples from the normal-pressured basin show B concentrations and B isotopic compositions ranging from 255 to 631 µM (0.6 to 1.5 times of seawater value) and from +29.1 to +42.7 per mil (relative to NIST SRM 951), respectively. A wider range is observed both for B concentrations (292 to 865 µM, 0.7 to 2.1 times of seawater value) and d11B values (+25.5 to +43.2 per mil) of the interstitial water in the over-pressured basin. The down-core distribution of B concentrations and d11B values in the interstitial waters are sensitive tracers for assessing various processes occurring in the sediment column, including boron adsorption/desorption reactions involving clay minerals and organic matter in sediments as well as fluid migration and mixing in certain horizons and in the sediment column. In the normal-pressured basin adsorption/desorption reactions in shallow sediments play the major role in controlling the B content and B isotopic composition of the interstitial water. In contrast, multiple processes affect the B content and d11B of the interstitial water in the over-pressured Ursa Basin. There, the stratigraphic level of the maxima of B and d11B correspond to seismic reflectors. The intruded fluids along the seismic reflector boundary from high to low-topography mix with local interstitial water. Fluid flow is inferred in the Blue Unit (a coarse sandstone layer, connecting the high- to low-pressured region) from the freshening of interstitial water in Ursa Basin Site U1322, and upward flow by the overpressure expels fluid from the overburden above the Blue Unit.

Pore water and solid phase geochemistry of sediment core US5B

Studies of authigenic phosphorus (P) minerals in marine sediments typically focus on authigenic carbonate fluorapatite, which is considered to be the major sink for P in marine sediments and can easily be semi-quantitatively extracted with the SEDEX sequential extraction method. The role of other potentially important authigenic P phases, such as the reduced iron (Fe) phosphate mineral vivianite (Fe(II)3(PO4)*8H2O) has so far largely been ignored in marine systems. This is, in part, likely due to the fact that the SEDEX method does not distinguish between vivianite and P associated with Fe-oxides. Here, we show that vivianite can be quantified in marine sediments by combining the SEDEX method with microscopic and spectroscopic techniques such as micro X-ray fluorescence (µXRF) elemental mapping of resin-embedded sediments, as well as scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) and powder X-ray diffraction (XRD). We further demonstrate that resin embedding of vertically intact sediment sub-cores enables the use of synchrotron-based microanalysis (X-ray absorption near-edge structure (XANES) spectroscopy) to differentiate between different P burial phases in aquatic sediments. Our results reveal that vivianite represents a major burial sink for P below a shallow sulfate/methane transition zone in Bothnian Sea sediments, accounting for 40-50% of total P burial. We further show that anaerobic oxidation of methane (AOM) drives a sink-switching from Fe-oxide bound P to vivianite by driving the release of both phosphate (AOM with sulfate and Fe-oxides) and ferrous Fe (AOM with Fe-oxides) to the pore water allowing supersaturation with respect to vivianite to be reached. The vivianite in the sediment contains significant amounts of manganese (~4-8 wt.%), similar to vivianite obtained from freshwater sediments. Our results indicate that methane dynamics play a key role in providing conditions that allow for vivianite authigenesis in coastal surface sediments. We suggest that vivianite may act as an important burial sink for P in brackish coastal environments worldwide.

Physical oceanography, pore water chemistry and water column methane turover rates during POLARSTERN cruise ANT-XXIX/4

Recent studies have suggested that the marine contribution of methane from shallow regions and melting marine terminating glaciers may have been underestimated. Here we report on methane sources and potential sinks associated with methane seeps in Cumberland Bay, South Georgia's largest fjord system. The average organic carbon content in the upper 8 meters of the sediment is around 0.65 wt.%; this observation combined with Parasound data suggest that the methane gas accumulations probably originate from peat-bearing sediments currently located several tens of meters below the seafloor. Only one of our cores indicates upward advection; instead most of the methane is transported via diffusion. Sulfate and methane flux estimates indicate that a large fraction of methane is consumed by anaerobic oxidation of methane (AOM). Carbon cycling at the sulfate-methane transition (SMT) results in a marked fractionation of the d13C-CH4 from an estimated source value of -65 per mil to a value as low as -96 per mil just below the SMT. Methane concentrations in sediments are high, especially close to the seepage sites (~40 mM); however, concentrations in the water column are relatively low (max. 58 nM) and can be observed only close to the seafloor. Methane is trapped in the lowermost water mass, however, measured microbial oxidation rates reveal very low activity with an average turnover of 3.1 years. We therefore infer that methane must be transported out of the bay in the bottom water layer. A mean sea-air flux of only 0.005 nM/m²/s confirms that almost no methane reaches the atmosphere.

Contents of water, sulphur, total organic and inorganic carbon, XRF counts of Ti, S and Ca and radiocarbon ages of sediment core Co1008 from Skua Lake, Rauer Group, East Antarctica

Limited information on the East Antarctic Ice Sheet (EAIS) geometry during Marine Isotope Stage 3 (MIS 3; 60-25 ka) restricts our understanding of its behaviour during periods of climate and sea level change. Ice sheet models forced by global parameters suggest an expanded EAIS compared to the Holocene during MIS 3, but field evidence from East Antarctic coastal areas contradicts such modelling, and suggests that the ice sheet margins were no more advanced than at present. Here we present a new lake sediment record, and cosmogenic exposure results from bedrock, which confirm that Rauer Group (eastern Prydz Bay) was ice-free for much of MIS 3. We also refine the likely duration of the Last Glacial Maximum (LGM) glaciation in the region. Lacustrine and marine sediments from Rauer Group indicate the penultimate period of ice retreat predates 50 ka. The lacustrine record indicates a change from warmer/wetter conditions to cooler/drier conditions after ca. 35 ka. Substantive ice sheet re-advance, however, may not have occurred until much closer to 20 ka. Contemporary coastal areas were still connected to the sea during MIS 3, restricting the possible extent of grounded ice in Prydz Bay on the continental shelf. In contrast, relative sea levels (RSL) deduced from field evidence indicate an extra ice load averaging several hundred metres thicker ice across the Bay between 45 and 32 ka. Thus, ice must either have been thicker immediately inland (with a steeper ice profile), or there were additional ice domes on the shallow banks of the outer continental shelf. Further work is required to reconcile the differences between empirical evidence of past ice sheet histories, and the history predicted by ice sheet models from far-field temperature and sea level records.

Seawater carbonate chemistry, virioplankton and bacterioplankton in a shallow CO2-dominated hydrothermal vent (Panarea Island, Tyrrhenian Sea)

Gas hydrothermal vents are used as a natural analogue for studying the effects of CO2 leakage from hypothetical shallow marine storage sites on benthic and pelagic systems. This study investigated the interrelationships between planktonic prokaryotes and viruses in the Panarea Islands hydrothermal system (southern Tyrrhenian Sea, Italy), especially their abundance, distribution and diversity. No difference in prokaryotic abundance was shown between high-CO2 and control sites. The community structure displayed differences between fumarolic field and the control, and between surface and bottom waters, the latter likely due to the presence of different water masses. Bacterial assemblages were qualitatively dominated by chemo- and photoautotrophic organisms, able to utilise both CO2 and H2S for their metabolic requirements. From significantly lower virioplankton abundance in the proximity of the exhalative area together with particularly low Virus-to-Prokaryotes Ratio, we inferred a reduced impact on prokaryotic abundance and proliferation. Even if the fate of viruses in this particular condition remains still unknown, we consider that lower viral abundance could reflect in enhancing the energy flow to higher trophic levels, thus largely influencing the overall functioning of the system.