Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.

Seawater carbonate chemistry and nutrients measured on water bottle samples during the International Siberian Shelf Study 2008 (ISSS-08) in the Laptev, East Siberian and Chukchi Seas

The motivation for ISSS-08 was to alleviate the scarcity of observational data on transport and processing of water, sediment and carbon on the East Siberian Arctic Shelves (ESAS). The region is of particular interest from the perspective of carbon-climate couplings as it has witnessed a 4°C springtime positive temperature anomaly for 2000-2005 compared with preceding decades. A complex sampling program was accomplished during the 50-days ISSS-08 cruise August - September 2008 by participants from 12 organizations in Russia, Sweden, UK and USA.

Stable Isotope composition of particulate organic matter and fauna in a deep Mediterranean cold-water coral bank

Cold-water corals (CWC) are frequently reported from deep sites with locally accelerated currents that enhance seabed food particle supply. Moreover, zooplankton likely account for ecologically important prey items, but their contribution to CWC diet remains unquantified. We investigated the benthic food web structure of the recently discovered Santa Maria di Leuca (SML) CWC province (300 to 1100 m depth) located in the oligotrophic northern Ionian Sea. We analyzed stable isotopes (delta13C and delta15N) of the main consumers (including ubiquitous CWC species) exhibiting different feeding strategies, zooplankton, suspended particulate organic matter (POM) and sedimented organic matter (SOM). Zooplankton and POM were collected 3 m above the coral colonies in order to assess their relative contributions to CWC diet. The delta15N of the scleractinians Desmophyllum dianthus, Madrepora oculata and Lophelia pertusa and the gorgonian Paramuricea cf. macrospinawere consistent with a diet mainly composed of zooplankton. The antipatharian Leiopathes glaberrima was more 15N- depletedthan other cnidarians, suggesting a lower contribution of zooplankton to its diet. Our delta13C data clearly indicate that the benthic food web of SML is exclusively fuelled by carbon of phytoplanktonic origin. Nevertheless, consumers feeding at the water sediment interface were more 13C-enriched than consumers feeding above the bottom (i.e. living corals and their epifauna). This pattern suggests that carbon is assimilated via 2 trophic pathways: relatively fresh phytoplanktonic production for 13C-depleted consumers and more decayed organic matter for 13C-enriched consumers. When the delta13C values of consumers were corrected for the influence of lipids (which are significantly 13C-depleted relative to other tissue components), our conclusions remained unchanged, except in the case of L. glaberrima which could assimilate a mixture of zooplankton and resuspended decayed organic matter.

Bulk sediment characteristics and geomicrobiology of sediment core 5022-1J from Laguna Potrok Aike, southern Patagonia

Living microorganisms inhabit every environment of the biosphere but only in the last decades their importance governing biochemical cycles in deep sediments has been widely recognized. Most investigations have been accomplished in the marine realm whereas there is a clear paucity of comparable studies in lacustrine sediments. One of the main challenges is to define geomicrobiological proxies that can be used to identify different microbial signals in the sediments. Laguna Potrok Aike, a maar lake located in Southeastern Patagonia, has an annually not stratifying cold water column with temperatures ranging between 4 and 10 °C, and most probably an anoxic water/sediment interface. These unusual features make it a peculiar and interesting site for geomicrobiological studies. Living microbial activity within the sediments was inspected by the first time in a sedimentary core retrieved during an ICDP-sponsored drilling operation. The main goals to study this cold subsaline environment were to characterize the living microbial consortium; to detect early diagenetic signals triggered by active microbes; and to investigate plausible links between climate and microbial populations. Results from a meter long gravity core suggest that microbial activity in lacustrine sediments can be sustained deeper than previously thought due to their adaptation to both changing temperature and oxygen availability. A multi-proxy study of the same core allowed defining past water column conditions and further microbial reworking of the organic fraction within the sediments. Methane content shows a gradual increase with depth as a result of the fermentation of methylated substrates, first methanogenic pathway to take place in the shallow subsurface of freshwater and subsaline environments. Statistical analyses of DGGE microbial diversity profiles indicate four clusters for Bacteria reflecting layered communities linked to the oxidant type whereas three clusters characterize Archaea communities that can be linked to both denitrifiers and methanogens. Independent sedimentary and biological proxies suggest that organic matter production and/or preservation have been lower during the Medieval Climate Anomaly (MCA) coinciding with a low microbial colonization of the sediments. Conversely, a reversed trend with higher organic matter content and substantial microbial activity characterizes the sediments deposited during the Little Ice Age (LIA). Thus, the initial sediments deposited during distinctive time intervals under contrasting environmental conditions have to be taken into account to understand their impact on the development of microbial communities throughout the sediments and their further imprint on early diagenetic signals.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Bitumoids and methane in bottom sediments of the northeast Black Sea

Complex investigations of recent and ancient Black Sea sediments from the outer shelf, continental slope, and deep-water basin of the Russian Black Sea sector have been carried out. Samples were collected during Cruise 100 of R/V Professor Shtokman organized by the P.P. Shirshov Institute of Oceanology (March 2009) and expedition of UZHMORGEO (summer 2006). Rates of the main anaerobic processes during diagenesis (sulfate reduction, dark CO2 assimilation, methanogenesis, and methane oxidation) were studied for the first time in sediment cores of the studied area. Two peaks in the rate of microbial processes and two sources of these processes were identified: the upper peak near the water-sediment contact is related to solar energy (OM substrate of the water column) and the lower peak at the base of ancient Black Sea sediments with high(>1 mmol) methane concentration related to energy of anaerobic methane oxidation. New labile OM formed during this process is utilized by other groups of microorganisms. According to experimental data, daily rate of anaerobic methane oxidation is many times higher than that of methanogenesis, which unambiguously indicates migration nature of the main part of methane.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Geochemistry on ferromanganese crusts and nodules from Green Bay, Lake Michigan

The differential solubility of ferromanganese oxides can lead to stratigraphic separation of iron and manganese. Results of chemical analysis of a sequence of ferromanganese nodules overlying iron-rich crusts in northern Green Bay show that selec¬tive ion transport is important in concentrating manganese and associated trace elements near the oxygenated water-sediment interface. Manganese carbonate, which cements ferromanganese nodules, occurs in dark-gray silty sands that are located adjacent to the organic-rich muds of southern Green Bay. These muds contain an average of approximately 3.5 ppm (6x10-5M) interstitial Mn with 2.8 meq/l carbonate alkalinity. Thermodynamic calculation shows that interstitial water approaches equilibrium with MnCO3 in the upper 10 cm of sediment. This carbonate has a composition (Mn73Ca22Fe5)CO3 and has been identified as rhodochrosite.

Illustrations of manganese nodules dredged from the Upper Jarvis Inlet

Manganese-iron oxide concretions are presently forming on Patrick Sill in upper Jervis Inlet. The marine geology of Patrick Sill and the adjoining basins (Queen's Reach and Princess Royal Reach) was studied to define the environment in which the concretions form. The river at the inlet head is the principal source of sediment to the upper basin. The average grain size of surficial bottom sediments within this basin decreases uniformly with distance from the source. Patrick Sill separates the upper from the lower basin. The sediment distribution pattern within the lower basin differs markedly from the upper basin as there is no dominant source of material but rather many localized sources. Abundant shallow marine faunal remains recovered in deep water sediment samples indicate that sediments deposited as deltas off river and stream mouths periodically slump to the basin floors. Geologic and optical turbidity information for the upper basin can best be explained by slumping from the delta at the inlet head with the initiation of turbidity or density currents. Patrick Sill appears to create a downstream barrier to this flow. The mineralogy of the bottom sediments indicates derivation from a granitic terrain. If this is so, the sediments presently being deposited in both basins are reworked glacial materials initially derived by glacial action outside the present watershed. Upper Jervis Inlet is mapped as lying within a roof pendant of pre-batholithic rocks, principally slates. Patrick Sill is thought to be a bedrock feature mantled with Pleistocene glacial material. The accumulation rate of recent sediments on the sill is low especially in the V-notch or medial depression. The manganese-iron oxide concretions are forming within the depression and apparently nowhere else in the study area. Also forming within the depression are crusts of iron oxide and what are tentatively identified as glauconite-montmorillonoid pellets. The concretions are thought to form by precipitation of manganese-iron oxides on pebbles and cobbles lying at the sediment water interface. The oxide materials are mobile in the reducing environment of the underlying clayey-sand sediment but precipitate on contact with the oxygenating environment of the surficial sediments. The iron crusts are thought to be forming on extensive rocky surfaces above the sediment water interface. The overall appearance and evidence of rapid formation of the crusts suggests they formed from a gel in sea water. Reserves of manganese-iron concretions on Patrick Sill were estimated to be 117 metric tons. Other deposits of concretions have recently been found in other inlets and in the Strait of Georgia but, to date, the extent of these has not been determined.

Results of biogeochemical studies in the Russian Arctic seas: isotope and radioisotope data

Comprehensive biogeochemical studies including determination of isotopic composition of organic carbon in both suspended matter and surface layer (0-1 cm) bottom sediments (more than 260 determinations of d13C-Corg) were carried out for five Arctic shelf seas: White, Barents, Kara, East Siberian, and Chukchi Seas. The aim of this study is to elucidate causes that change isotopic composition of particulate organic carbon at the water-sediment boundary. It is shown that isotopic composition of organic carbon in sediments from seas with high river run-off (White, Kara, and East Siberian Seas) does not inherit isotopic composition of organic carbon in particles precipitating from the water column, but is enriched in 13C. Seas with low river run-off (Barents and Chukchi Seas) show insignificant difference between d13C-Corg values in both suspended load and sediments because of low content of isotopically light allochthonous organic matter in suspended matter. Biogeochemical studies with radioisotope tracers (14CO2, 35S, and 14CH4) revealed existence of specific microbial filter formed from heterotrophic and autotrophic organisms at the water-sediment boundary. This filter prevents mass influx of products of organic matter decomposition into the water column, as well as reduces influx of OM contained in suspended matter from water into sediments.

(Fig 2, page 399), Distribution of Fe and Mn in ferromanganese nodules of the Eningi-Lampi Lake, Russia

The distribution of Mn and Fe in water, sediments, hydroxide nodules and crusts of Eningi-Lampi ore-bearing lake is regular, and concordant from the source to the areas of accumulation of these components. Mn-Fe hydroxide nodules and crusts occur at the water-sediment interface, and more rarely in the upper (0-5 cm) film of brown watery mud. The leading role in the formation of Mn-Fe nodules and crusts is played by the chemosorption and auto-catalytic oxidation in the course of interaction of component-bearing solutions with active surfaces. This is considered to be the basic process for the model of ferromanganese ore formation in recent basins. Despite the differences in the physico-geographical and geochemical characteristics of lakes, mediterranean seas and oceans, the formation of ferromanganese hydroxide nodules and crusts in these basins may be explained by this model.