Mineralogical and isotopic compositions of ODP Hole 107-650A

Red-brown dolomitic claystones overlay the Marsili Basin basaltic basement at ODP Site 650. Sequential leaching experiments reveal that most of the elements considered to have a hydrothermal or hydrogenous origin in a marine environment, such as Fe, Cu, Zn, Pb, Co, Ni, are present mainly in the aluminosilicate fraction of the dolomitic claystones. Their vertical distribution, content and partitioning chemistry of trace elements, and REE patterns suggest enhanced terrigenous input during dolomite formation, but no significant hydrothermal influence from the underlying basaltic basement. Positive correlations in the C and O isotopes in the dolomites reflect complex conditions during the dolomitization. The stable isotopes can be controlled in part by temperature variations during the dolomitization. Majority of the samples, however, form a trend that is steeper than expected for only temperature control on the C and O isotopes. The latter indicates possible isotopic heterogeneity in the proto-carbonate that can be related to arid climatic conditions during the formation of the basal dolomitic claystones. In addition, the dolostones stable isotopic characteristics can be influenced by diagenetic release of heavier delta18O from clay dehydration and/or alteration of siliciclastic material. Strontium and Pb isotopic data reveal that the non-carbonate fraction, the "dye" of the dolomitic claystones, is controlled by Saharan dust (75%-80%) and by material with isotopic characteristics similar to the Aeolian Arc volcanoes (20%-25%). The non-carbonate fraction of the calcareous ooze overlying the dolomitic claystones has a Sr and Pb isotopic composition identical to that of the dolomitic claystones, indicating that no change in the input sources to the sedimentary basin occurred during and after the dolomitization event. Combination of climato-tectonic factors most probably resulted in suitable conditions for dolomitization in the Marsili and the nearby Vavilov Basins. The basal dolomitic claystone sequence was formed at the initiation of the opening of the Marsili Basin (~2 Ma), which coincided with the consecutive glacial stage. The glaciation caused arid climate and enhanced evaporation that possibly contributed to the stable isotope variations in the proto-carbonate. The conductive cooling of the young lithosphere produced high heat flow in the region, causing low-temperature passive convection of pore waters in the basal calcareous sediment. We suggest that this pumping process was the major dolomitization mechanism since it is capable of driving large volumes of seawater (the source of Mg2+) through the sediment. The red-brown hue of the dolomitic claystones is terrigenous contribution of the glacially induced high eolian influx and was not hydrothermally derived from the underlying basaltic basement. The detailed geochemical investigation of the basal dolomitic sequence indicates that the dolomitization was most probably related to complex tectono-climatic conditions set by the initial opening stages of the Marsili Basin and glaciation.

Spatial compartmentalization of free radical formation and mitochondrial heterogeneity in bivalve gills revealed by live-imaging techniques, supplementary material

Live-imaging techniques (LIT) utilize target-specific fluorescent dyes to visualize biochemical processes using confocal and multiphoton scanning microscopy, which are increasingly employed as non-invasive approach to physiological in-vivo and ex-vivo studies. Here we report application of LIT to bivalve gills for ex-vivo analysis of gill physiology and mapping of reactive oxygen (ROS) and nitrogen (RNS) species formation in the living tissue. Our results indicate that H2O2, HOO. and ONOO- radicals (assessed through C-H2DFFDA staining) are mainly formed within the blood sinus of the filaments and are likely to be produced by hemocytes as defense against invading pathogens. The oxidative damage in these areas is controlled by enhanced CAT (catalase) activities recorded within the filaments. The outermost areas of the ciliated epithelial cells composing the filaments, concentrated the highest mitochondrial densities (MTK Deep Red 633 staining) and the most acidic pH values (as observed with ageladine-a). These mitochondria have low (depolarized) membrane potentials (D psi m) (JC-1 staining), suggesting that the high amounts of ATP required for ciliary beating may be in part produced by non-mitochondrial mechanisms, such as the enzymatic activity of an ATP-regenerating kinase. Nitric oxide (NO, DAF-2DA staining) produced in the region of the peripheral mitochondria may have an effect on mitochondrial electron transport and possibly cause the low membrane potential. High DAF-2DA staining was moreover observed in the muscle cells composing the wall of the blood vessels where NO may be involved in regulating blood vessel diameter. On the ventral bend of the gills, subepithelial mucus glands (SMG) contain large mucous vacuoles showing higher fluorescence intensities for O2.- (DHE staining) than the rest of the tissue. Given the antimicrobial properties of superoxide, release of O2.- into the mucus may help to avoid the development of microbial biofilms on the gill surface. However, cells of the ventral bends are paying a price for this antimicrobial protection, since they show significantly higher oxidative damage, according to the antioxidant enzyme activities and the carbonyl levels, than the rest of the gill tissue. This study provides the first evidence that one single epithelial cell may contain mitochondria with significantly different membrane potentials. Furthermore, we provide new insight into ROS and RNS formation in ex-vivo gill tissues which opens new perspectives for unraveling the different ecophysiological roles of ROS and RNS in multifunctional organs such as gills.

Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.

(Table 1) Lipid and organochlorine content in blood of common eiders (Somateria mollissima) in Svalbard

Female common eiders (Somateria mollissima) starve during the nesting stage and may lose 30-45% of their initial body mass, mostly through lipid mobilization. In this study, the effects of fasting on the blood concentrations of three lipid-soluble organochlorines (OCs: polychlorinated biphenyl [PCB]-153; 1-dichloro-2,2-bis (p-chlorophenyl) ethylene [p,p'-DDE]; and hexachlorobenzene [HCB]) were examined in eiders breeding in the high Arctic. Blood samples were taken from females (n = 47) at day 5 and day 20 of the incubation period. The mean wet weight concentrations of PCB-153 and p,p'-DDE increased strongly between day 5 and day 20 (3.6 and 8.2-fold, respectively), while HCB increased less (1.7-fold). There was a strong negative association between daily increase in PCB-153 and clutch size, and a weaker relationship for p,p'-DDE, suggesting that maternal transfer to the eggs is a significant pathway of elimination of OCs in eiders. Moreover, poor body condition (body mass controlled for body size) late in the incubation period was associated with strong daily increase of both p,p'-DDE and PCB-153, which may suggest that the release of these compounds increases when lipid reserves become depleted. For HCB, the increase was mainly associated with increase in blood lipid concentrations, and weakly to the amount of burned lipids. The causes for the differences between the compounds are, however, poorly understood. Although the absolute levels of OCs in eiders were relatively low, their rapid build-up during incubation is worrying as it coincides with poor body condition and weakened immune systems.

Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

Radiogenic isotope trace composition of the Labrador Sea

Geological reconstructions and general circulation models suggest that the onset of both Northern Hemisphere glaciation, 2.7 Myr ago, and convection of Labrador Sea Water (LSW) were caused by the closure of the Panama Gateway ~4.5 Myr ago. Time series data that have been obtained from studies of ferromanganese crusts from the northwestern Atlantic suggest that radiogenic isotopes of intermediate ocean residence time (Pb and Nd) can serve as suitable tracers to reconstruct these events. However, it has been unclear until now as to whether the changes that have been observed in isotope composition at this time are the result of increased thermohaline circulation or due to the effects of increased glacial weathering. In this paper we adopt a box model approach to demonstrate that the shifts in radiogenic isotope compositions are unlikely to be due to changes in convection in LSW but can be explained in terms of increases of erosion levels due to the glaciation of Greenland and Canada. Furthermore, we provide experimental evidence for the incongruent release of a labile fraction of strongly radiogenic Pb and nonradiogenic Nd from continental detritus eroding into the Labrador Sea. This can be attributed to the glacial weathering of old continents and accounts for the paradox that one of the areas of the world most deficient in radiogenic Pb should provide such a rich supply of radiogenic Pb to the oceans. An important general conclusion is that the compositions of radiogenic isotopes in seawater are not always a reflection of their continental sources. Perhaps more importantly, the transition from chemical weathering to mechanical erosion is likely to result in significant variations in radiogenic tracers in seawater.

Zooplankton data of M83/1

Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.

Biogeochemistry of mesocosm experiments in the tropical Pacific and Atlantic Ocean

Oxygen-deficient waters in the ocean, generally referred to as oxygen minimum zones (OMZ), are expected to expand as a consequence of global climate change. Poor oxygenation is promoting microbial loss of inorganic nitrogen (N) and increasing release of sediment-bound phosphate (P) into the water column. These intermediate water masses, nutrient-loaded but with an N deficit relative to the canonical N:P Redfield ratio of 16:1, are transported via coastal upwelling into the euphotic zone. To test the impact of nutrient supply and nutrient stoichiometry on production, partitioning and elemental composition of dissolved (DOC, DON, DOP) and particulate (POC, PON, POP) organic matter, three nutrient enrichment experiments were conducted with natural microbial communities in shipboard mesocosms, during research cruises in the tropical waters of the southeast Pacific and the northeast Atlantic. Maximum accumulation of POC and PON was observed under high N supply conditions, indicating that primary production was controlled by N availability. The stoichiometry of microbial biomass was unaffected by nutrient N:P supply during exponential growth under nutrient saturation, while it was highly variable under conditions of nutrient limitation and closely correlated to the N:P supply ratio, although PON:POP of accumulated biomass generally exceeded the supply ratio. Microbial N:P composition was constrained by a general lower limit of 5:1. Channelling of assimilated P into DOP appears to be the mechanism responsible for the consistent offset of cellular stoichiometry relative to inorganic nutrient supply and nutrient drawdown, as DOP build-up was observed to intensify under decreasing N:P supply. Low nutrient N:P conditions in coastal upwelling areas overlying O2-deficient waters seem to represent a net source for DOP, which may stimulate growth of diazotrophic phytoplankton. These results demonstrate that microbial nutrient assimilation and partitioning of organic matter between the particulate and the dissolved phase are controlled by the N:P ratio of upwelled nutrients, implying substantial consequences for nutrient cycling and organic matter pools in the course of decreasing nutrient N:P stoichiometry.

Carbon sources in the North Sea evaluated by means of carbon isotope tracers

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sedi- ments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indi- cates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of meta- bolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long- term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

Ground ice hydrochemical composition of permafrost core ICDP5011-3

The continuous sediment record from Lake El'gygytgyn in the northeastern Eurasian Arctic spans the last 3.6 Ma and for much of this time permafrost dynamics and lake level changes have likely played a crucial role for sediment delivery to the lake. Changes in the ground-ice hydrochemical composition (d18O, dD, pH, electrical conductivity, Na+, Mg2+, Ca2+, K+, HCO3-, Cl-, SO4-) of a 141 m long permafrost record from the western crater plain are examined to reconstruct repeated periods of freeze and thaw at the lake edge. Stable water isotope and major ion records of ground ice in the permafrost reflect both a synsedimentary palaeo-precipitation signal preserved in the near-surface permafrost (0.0-9.1 m core depth) and a post-depositional record of thawing and refreezing in deeper layers of the core (9.1-141.0 m core depth). These lake marginal permafrost dynamics were controlled by lake level changes that episodically flooded the surfaces and induced thaw in the underlying frozen ground. During times of lake level fall these layers froze over again. At least three cycles of freeze and thaw are identified and the hydrochemical data point to a vertical and horizontal talik refreezing through time. Past permafrost thaw and freeze may have destabilised the basin slopes of Lake El'gygytgyn and this has probably promoted the release of mass movements from the lake edge to the deeper basin as known from frequently occurring turbidite layers in the lake sediment column.