Anaerobic oxidation of methane and sulphate reduction rates, hydrocarbons, sulphate and sulphide concentrations of sediment cores from the Larsen B embayment at the eastern site of the Antarctic Peninsula

First videographic indication of an Antarctic cold seep ecosystem was recently obtained from the collapsed Larsen B ice shelf, western Weddell Sea (Domack et al., 2005). Within the framework of the R/V Polarstern expedition ANTXXIII-8, we revisited this area for geochemical, microbiological and further videographical examinations. During two dives with ROV Cherokee (MARUM, Bremen), several bivalve shell agglomerations of the seep-associated, chemosynthetic clam Calyptogena sp. were found in the trough of the Crane and Evans glacier. The absence of living clam specimens indicates that the flux of sulphide and hence the seepage activity is diminished at present. This impression was further substantiated by our geochemical observations. Concentrations of thermogenic methane were moderately elevated with 2 µM in surface sediments of a clam patch, increasing up to 9 µM at a sediment depth of about 1 m in the bottom sections of the sediment cores. This correlated with a moderate decrease in sulphate from about 28 mM at the surface down to 23.4 mM, an increase in sulphide to up to 1.43 mM and elevated rates of the anaerobic oxidation of methane (AOM) of up to 600 pmol cm**-3 d**-1 at about 1 m below the seafloor. Molecular analyses indicate that methanotrophic archaea related to ANME-3 are the most likely candidates mediating AOM in sediments of the Larsen B seep.

Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Chemistry of primary and secondary phases in intraplate basalts and volcaniclastic sediments at DSDP Leg 89 Holes

Electron microprobe data are presented for clinopyroxenes, plagioclases, palagonites, smectites, celadonites, and zeolites in Hole 462A sheet-flow basalts and Site 585 volcaniclastic sediments. Glomerocrystic clinopyroxenes in Hole 462A are predominantly Ti-poor augites with minor fractionation to ferroaugites in rim portions. Quenched plumose clinopyroxenes show considerable variation from Ca-rich to Ca-poor augites, although all are characterized by being Tirich and Cr-poor relative to the glomerocrysts. Two differentiated series of Site 585 pyroxene compositions, calcic augite and diopside-salite, demonstrate the coexistence, in the vitric and lithic clasts, of tholeiitic and alkali basalt types, respectively. Plagioclase compositions in all samples are mainly labradorites, although some zoned Hole 462A glomerocrysts range from An73 to An20 and are characterized by high Mg and Fe contents in the more calcic varieties. The K content of the plagioclases is highest in the more sodic crystals, although the overall higher orthoclase component of Site 585 plagioclases reflects the generally higher bulk-rock K content. The compositions of both secondary smectites and celadonites are similar irrespective of the alteration location (glass, matrix, vesicles, etc.), although brown smectites replacing interstitial glass have marginally higher total Fe contents than pale green and yellow smectites. Analyzed zeolites are mainly phillipsites with variable alkali content, and, together with associated celadonite, represent late-stage alteration repositories for K under mildly oxidizing conditions. The compositions of both early and late secondary minerals are typical of those formed by the submarine alteration of basaltic rocks at low temperatures.

Geochemistry and isotopic ratios of boninites and related rocks of the Izu-Bonin Forearc

Twenty-six samples representing the wide range of lithologies (low- and intermediate-Ca boninites and bronzite andesites, high-Ca boninites, basaltic andesites-rhyolites) drilled during Leg 125 at Sites 782 and 786 on the Izu-Bonin outer-arc high have been analyzed for Sr, Nd, and Pb isotopes. Nd-Sr isotope covariations show that most samples follow a trend parallel to a line from Pacific MORB mantle (PMM) to Pacific Volcanogenic sediment (PVS) but displaced slightly toward more radiogenic Sr. Pb isotope covariations show that all the Eocene-Oligocene samples plot along the Northern Hemisphere Reference Line, indicating little or no Pb derived from subducted pelagic sediment in their source. Two young basaltic andesite clasts within sediment do have a pelagic sediment signature but this may have been gained by alteration rather than subduction. In all isotopic projections, the samples form consistent groupings: the tholeiites from Site 782 and Hole 786A plot closest to PMM, the boninites and related rocks from Sites 786B plot closest to PVS, and the boninite lavas from Hole 786A and late boninitic dikes from Hole 786B occupy an intermediate position. Isotope-trace element covariations indicate that these isotopic variations can be explained by a three-component mixing model. One component (A) has the isotopic signature of PMM but is depleted in the more incompatible elements. It is interpreted as representing suboceanic mantle lithosphere. A second component (B) is relatively radiogenic (epsilon-Nd = ca 4-6; 206Pb/204Pb = ca 19.0-19.3; epsilon-Sr = ca -10 to -6)). Its trace element pattern has, among other characteristics, a high Zr/Sm ratio, which distinguishes it from the ìnormalî fluid components associated with subduction and hotspot activity. There are insufficient data at present to tie down its origin: probably it was either derived from subducted lithosphere or volcanogenic sediment fused in amphibolite facies; or it represents an asthenospheric melt component that has been fractionated by interaction with amphibole-bearing mantle. The third component (C) is characterized by high contents of Sr and high epsilon-Sr values and is interpreted as a subducted fluid component. The mixing line on a diagram of Zr/Sr against epsilon-Sr suggests that component C may have enriched the lithosphere (component A) before component B. These components may also be present on a regional basis but, if so, may not have had uniform compositions. Only the boninitic series from nearby Chichijima would require an additional, pelagic sediment component. In general, these results are consistent with models of subduction of ridges and young lithosphere during the change from a ridge-transform to subduction geometry at the initiation of subduction in the Western Pacific.

Composition and sorption capacity of oceanic and marine ferromanganese nodules

Experimental data obtained show that oceanic and marine ferromanganese nodules and crusts are natural ion-exchangers. Exchange capacity of oceanic ferromanganese aggregates is much higher than that of shallow-water marine ones, whereas reactivities of exchange cations (Na, K, Ca, and Mg) are almost equal in both.

Paleoclimate record combinatio of speleothems and of sediment core GeoB3910-2

A substantial strengthening of the South American monsoon system (SAMS) during Heinrich Stadials (HS) points toward decreased cross-equatorial heat transport as the main driver of monsoonal hydroclimate variability at millennial time-scales. In order to better constrain the exact timing and internal structure of HS1 over tropical South America we assessed two precisely dated speleothem records from central-eastern and northeastern Brazil in combination with two marine records of terrestrial organic and inorganic matter input into the western equatorial Atlantic. During HS1 we recognize at least two events of widespread intensification of the SAMS across the entire region influenced by the South Atlantic Convergence Zone (SACZ) at 16.11-14.69 kyr BP and 18.1-16.66 kyr BP (labeled as HS1a and HS1c, respectively), separated by a dry excursion from 16.66-16.11 kyr BP (HS1b). In view of the spatial structure of precipitation anomalies, the widespread increase of monsoon precipitation over the SACZ domain was termed 'Mega-SACZ'.

Composition of native Cu, Cu isotope and mineral analysis from different samples of ODP and DSDP

Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.

Development of bacterial and archaeal communities in erupted subsurface muds at the Håkon Mosby mud volcano

The microbial oxidation of methane controls the emission of the greenhouse gas methane from the ocean floor. However, some seabed structures such as mud volcanoes have leaky microbial methane filters and can be important sources of methane. We investigated the disturbance and recovery of a methanotrophic mud volcano microbiome (Håkon Mosby mud volcano, 1250 m water depth), to assess time scales of community succession and function in the natural deep-sea environment. We analyzed 10 surface and 5 subsurface sediment samples across HMMV mud flows from most recently discharged subsurface muds towards old consolidated muds as well as one reference site (REF) located approximately 0.5 km outside of the HMMV. Surface samples were obtained in 2003, 2009 and 2010. The surface of the new mud flows at the geographical center was sampled in 2009 and 2010. Around 100 m south of the center, we sampled more consolidated aged muds in 2003 and 2010. Old mud flows were sampled around 300 m southeast and 100 m north of the geographical center in 2003, 2009 and 2010. Surface sediment samples (0-20 cm) were recovered either by TV-guided Multicorer or by push cores using the remotely operated vehicle Quest (Marum, University Bremen). Subsurface sediments of all zones (>2 m below sea floor) were obtained in 2003 by gravity corer. After recovery, sediments were immediately subsampled in a refrigerated container (0°C) and further processed for biogeochemical analyses or preserved at -20°C for later DNA analyses. Our study show that freshly erupted muds hosted heterotrophic deep subsurface communities, which were replaced by surface communities within a few years of exposure. Aerobic methanotrophy was established at the top surface layer within less than a year, followed by anaerobic methanotrophy, sulfate reduction and finally thiotrophy. Our data indicate that it takes decades in cold environments before efficient methanotrophic communities establish to control methane emission. The observed succession provides insights to the response time of complex deep-sea communities to seafloor disturbances.